JPS6353139B2 - - Google Patents
Info
- Publication number
- JPS6353139B2 JPS6353139B2 JP5899480A JP5899480A JPS6353139B2 JP S6353139 B2 JPS6353139 B2 JP S6353139B2 JP 5899480 A JP5899480 A JP 5899480A JP 5899480 A JP5899480 A JP 5899480A JP S6353139 B2 JPS6353139 B2 JP S6353139B2
- Authority
- JP
- Japan
- Prior art keywords
- glass
- copper
- coloring
- staining agent
- powder
- 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.)
- Expired
Links
- 239000011521 glass Substances 0.000 claims description 134
- 239000003795 chemical substances by application Substances 0.000 claims description 110
- 238000010186 staining Methods 0.000 claims description 110
- 238000000034 method Methods 0.000 claims description 69
- 239000010410 layer Substances 0.000 claims description 62
- 239000000203 mixture Substances 0.000 claims description 54
- 239000000843 powder Substances 0.000 claims description 54
- 238000004040 coloring Methods 0.000 claims description 53
- 238000012546 transfer Methods 0.000 claims description 53
- 239000010949 copper Substances 0.000 claims description 50
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 43
- 229910052802 copper Inorganic materials 0.000 claims description 43
- DOVLHZIEMGDZIW-UHFFFAOYSA-N [Cu+3].[O-]B([O-])[O-] Chemical compound [Cu+3].[O-]B([O-])[O-] DOVLHZIEMGDZIW-UHFFFAOYSA-N 0.000 claims description 37
- 239000011347 resin Substances 0.000 claims description 33
- 229920005989 resin Polymers 0.000 claims description 33
- 150000003839 salts Chemical class 0.000 claims description 33
- 238000010304 firing Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 20
- -1 copper borate compound Chemical class 0.000 claims description 18
- 238000007639 printing Methods 0.000 claims description 17
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 15
- 229910052796 boron Inorganic materials 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 239000002270 dispersing agent Substances 0.000 claims description 14
- 239000000945 filler Substances 0.000 claims description 14
- 239000012790 adhesive layer Substances 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- 239000002585 base Substances 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- 238000004898 kneading Methods 0.000 claims description 7
- 239000003086 colorant Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 239000005749 Copper compound Substances 0.000 claims description 4
- 150000001880 copper compounds Chemical class 0.000 claims description 4
- 238000007649 pad printing Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 230000003247 decreasing effect Effects 0.000 claims 3
- FZQBLSFKFKIKJI-UHFFFAOYSA-N boron copper Chemical compound [B].[Cu] FZQBLSFKFKIKJI-UHFFFAOYSA-N 0.000 claims 2
- 239000010408 film Substances 0.000 description 72
- 239000005357 flat glass Substances 0.000 description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000002344 surface layer Substances 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- GDTSJMKGXGJFGQ-UHFFFAOYSA-N 3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound O1B([O-])OB2OB([O-])OB1O2 GDTSJMKGXGJFGQ-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000007447 staining method Methods 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 238000009472 formulation Methods 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 229920006267 polyester film Polymers 0.000 description 6
- 229910001432 tin ion Inorganic materials 0.000 description 6
- 229910021538 borax Inorganic materials 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- 238000007646 gravure printing Methods 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920006122 polyamide resin Polymers 0.000 description 4
- 235000010339 sodium tetraborate Nutrition 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- YZYDPPZYDIRSJT-UHFFFAOYSA-K boron phosphate Chemical compound [B+3].[O-]P([O-])([O-])=O YZYDPPZYDIRSJT-UHFFFAOYSA-K 0.000 description 3
- 229910000149 boron phosphate Inorganic materials 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- NCEXYHBECQHGNR-UHFFFAOYSA-N chembl421 Chemical compound C1=C(O)C(C(=O)O)=CC(N=NC=2C=CC(=CC=2)S(=O)(=O)NC=2N=CC=CC=2)=C1 NCEXYHBECQHGNR-UHFFFAOYSA-N 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000007667 floating Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 229910000464 lead oxide Inorganic materials 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000006072 paste Substances 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 229940100890 silver compound Drugs 0.000 description 3
- 150000003379 silver compounds Chemical class 0.000 description 3
- 238000010583 slow cooling Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 3
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- SFOQXWSZZPWNCL-UHFFFAOYSA-K bismuth;phosphate Chemical compound [Bi+3].[O-]P([O-])([O-])=O SFOQXWSZZPWNCL-UHFFFAOYSA-K 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000007602 hot air drying Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 230000007794 irritation Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 150000002688 maleic acid derivatives Chemical class 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 229920000609 methyl cellulose Polymers 0.000 description 2
- 239000001923 methylcellulose Substances 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 150000003606 tin compounds Chemical class 0.000 description 2
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 2
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LUEWUZLMQUOBSB-FSKGGBMCSA-N (2s,3s,4s,5s,6r)-2-[(2r,3s,4r,5r,6s)-6-[(2r,3s,4r,5s,6s)-4,5-dihydroxy-2-(hydroxymethyl)-6-[(2r,4r,5s,6r)-4,5,6-trihydroxy-2-(hydroxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-4,5-dihydroxy-2-(hydroxymethyl)oxan-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound O[C@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@@H](O[C@@H]2[C@H](O[C@@H](OC3[C@H](O[C@@H](O)[C@@H](O)[C@H]3O)CO)[C@@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O LUEWUZLMQUOBSB-FSKGGBMCSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- CBECDWUDYQOTSW-UHFFFAOYSA-N 2-ethylbut-3-enal Chemical compound CCC(C=C)C=O CBECDWUDYQOTSW-UHFFFAOYSA-N 0.000 description 1
- 235000007173 Abies balsamea Nutrition 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 208000002109 Argyria Diseases 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 229920002581 Glucomannan Polymers 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- 244000018716 Impatiens biflora Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920000715 Mucilage Polymers 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- QFVJLAYKIQBTGJ-UHFFFAOYSA-N [Cu+2].[Cu+2].[Cu+2].[Cu+2].[Cu+2].[Cu+2].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] Chemical compound [Cu+2].[Cu+2].[Cu+2].[Cu+2].[Cu+2].[Cu+2].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] QFVJLAYKIQBTGJ-UHFFFAOYSA-N 0.000 description 1
- DNLDJFJLZNETDB-UHFFFAOYSA-N [V+5].[V+5].[V+5].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] Chemical compound [V+5].[V+5].[V+5].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] DNLDJFJLZNETDB-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- KIQKNTIOWITBBA-UHFFFAOYSA-K antimony(3+);phosphate Chemical compound [Sb+3].[O-]P([O-])([O-])=O KIQKNTIOWITBBA-UHFFFAOYSA-K 0.000 description 1
- RCUAPGYXYWSYKO-UHFFFAOYSA-J barium(2+);phosphonato phosphate Chemical compound [Ba+2].[Ba+2].[O-]P([O-])(=O)OP([O-])([O-])=O RCUAPGYXYWSYKO-UHFFFAOYSA-J 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000679 carrageenan Substances 0.000 description 1
- 229920001525 carrageenan Polymers 0.000 description 1
- 235000010418 carrageenan Nutrition 0.000 description 1
- 229940113118 carrageenan Drugs 0.000 description 1
- 239000012461 cellulose resin Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- XZTWHWHGBBCSMX-UHFFFAOYSA-J dimagnesium;phosphonato phosphate Chemical compound [Mg+2].[Mg+2].[O-]P([O-])(=O)OP([O-])([O-])=O XZTWHWHGBBCSMX-UHFFFAOYSA-J 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
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- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229940046240 glucomannan Drugs 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 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
- YAFKGUAJYKXPDI-UHFFFAOYSA-J lead tetrafluoride Chemical compound F[Pb](F)(F)F YAFKGUAJYKXPDI-UHFFFAOYSA-J 0.000 description 1
- ZPPSOOVFTBGHBI-UHFFFAOYSA-N lead(2+);oxido(oxo)borane Chemical compound [Pb+2].[O-]B=O.[O-]B=O ZPPSOOVFTBGHBI-UHFFFAOYSA-N 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
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- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
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- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
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- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
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- XGFPOHQJFNFBKA-UHFFFAOYSA-B tetraaluminum;phosphonato phosphate Chemical compound [Al+3].[Al+3].[Al+3].[Al+3].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O XGFPOHQJFNFBKA-UHFFFAOYSA-B 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- CQDTUBLRLRFEJX-UHFFFAOYSA-N tricopper;diborate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]B([O-])[O-].[O-]B([O-])[O-] CQDTUBLRLRFEJX-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Surface Treatment Of Glass (AREA)
Description
本発明は金属コロイドによる着色ガラスの製造
方法であるステイニング法における特に銅とホウ
素等を含有するステイニング剤並びに該ステイニ
ング剤によるガラスの着色方法に関する新規な発
明に係るものである。
ガラスの着色方法であるステイニング法は、ガ
ラスの表面に銅或いは銀化合物の溶液、これらの
溶液とカオリン等の混合物或いは銅もしくは銀化
合物と樹脂等の混合物等を塗布して加熱すること
により、ガラスの表面層中のアルカリイオンと銅
イオン或いは銀イオンを交換した後に水素を含む
雰囲気中で還元することによつて、ガラスの表面
層のみを着色する方法としてよく知られ、例えば
銀化合物（硫化銀、硝酸銀、塩化銀等）を用いた
ものは銀ステイニング法といわれ黄色に着色する
こと、銅化合物（硫酸銅、硫化銅等）を用いたも
のは銅ステイニング法といわれ赤色に着色するこ
とがよく知られている。
かかるステイニング法において使用するステイ
ニング剤に、金化合物或いは銀化合物等の貴金属
化合物を使用することは、最近の貴金属類の価格
の異常な上昇によつて極めて高価なものとなり実
用に供するには問題がある。
従つて本発明者等はコスト面から実用性に富ん
だ上記銅ステイニング法に着目しその実用化に取
り組んだが、従来の銅ステイニング剤においては
着色剤として使用されている銅の化合物として例
えば硫化銅、塩化銅、硫酸銅等があるがこれら公
知のものでは未だ十分な発色が得られていない現
況に鑑み、これら銅ステイニング法及び銅ステイ
ニング剤の改良について種々研究を重ねた結果、
ステイニング剤における着色剤として銅の含ホウ
素酸塩組成物粉末を使用し、これをインク化して
使用すれば、ガラス表面での発色工程の際、ステ
イニング剤中のホウ素又はホウ素化合物が、ステ
イニング剤中からガラス表面へ導入される銅イオ
ンの移行を促進させる媒体になることを究明する
と共にガラスの着色効率が著しく高められること
を発見し遂に本発明を完成するに至つたものであ
る。
即ち本発明は、銅の含ホウ素酸塩組成物粉末
に、必要によりフイラーを加え、これに、樹脂バ
インダー、溶剤及び必要により分散剤を添加し、
これを混練してインク化してなることを特徴とす
るガラス着色用ステイニング剤に係り、また該ガ
ラス着色用ステイニング剤において銅１重量部に
対しホウ素が0.1〜1.0重量部の組成からなる銅の
含ホウ素酸塩組成物粉末を使用して、これを着色
すべきガラス表面に全面又は任意の図柄に塗布又
は印刷してステイニング剤の皮膜層を形成し、而
る後400℃〜800℃に加熱焼成してステイニング剤
の皮膜層中の銅をガラス表面層に導入させて発色
させることを特徴とするガラスの着色方法に関す
るものであり、更には上記ステイニング剤を着色
すべきガラスの表面へ施す工程が前記塗布、印刷
の方法による他に、ステイニング剤の印刷皮膜層
が形成された転写シートを用いて加熱加圧により
ガラス表面へ転写絵付する方法、或いはステイニ
ング剤の印刷皮膜層を形成した水溶性フイルムを
水面上に浮かべ、上方から着色すべきガラス物体
を押圧、沈降させて仮着させる方法等をも含むも
のである。
本発明における銅の含ホウ素酸塩組成物粉末と
しては、ホウ酸銅化合物粉末、例えば各種ホウ酸
銅、各種ホウ酸銅のアルカリ錯塩、アンモニア錯
塩、アミン錯塩等の粉末、或いはホウフツ化銅化
合物粉末、例えば各種ホウフツ化銅、各種ホウフ
ツ化銅のアルカリ錯塩、アンモニア錯塩、アミン
錯塩等の粉末や、更に又上記ホウ酸銅化合物粉末
と上記ホウフツ化銅化合物粉末との混合物等が任
意に使用できる。
上記各種ホウ酸銅としては例えば、テトラホウ
酸第１銅、テトラホウ酸第２銅、メタホウ酸第１
銅、メタホウ酸第２銅、過ホウ酸第２銅等の単独
又は２種以上の混合物等があり、
各種ホウ酸銅アルカリ塩としては、上記各種ホ
ウ酸銅とホウ酸ナトリウム、ホウ酸カリウム、又
はホウ酸リチウムとの錯塩等があり、
各種ホウ酸銅のアンモニア錯塩としては上記の
各種ホウ酸銅とアンモニア、ハロゲン化アンモニ
ウム、ホウ酸アンモニウム、炭酸アンモニウム、
硫酸アンモニウム等の錯塩があり、
各種ホウ酸銅のアミン塩としては、上記の各種
ホウ酸銅と第一級アミン、第二級アミン、第三級
アミン、ジアミン、トリアミン、ポリアミン、尿
素、アミン誘導体との錯塩、複塩等があり、
各種ホウフツ化銅としては、テトラフルオロホ
ウ酸第１銅、テトラフルオロホウ酸第２銅、オキ
シトリフルオロホウ酸第１銅、スルフアトオキシ
ホウ酸第１銅、ジヒロドキシジフルオロホウ酸第
２銅等があり、
各種ホウフツ化銅のアルカリ錯塩としては、上
記各種ホウフツ化銅とホウ酸ナトリウム、ホウ酸
カリウム、又はホウ酸リチウムとの錯塩があり、
各種ホウフツ化銅のアンモニア錯塩としては、
上記の各種ホウフツ化銅とアンモニア、ハロゲン
化アンモニウム、ホウ酸アンモニウム、炭酸アン
モニウム、硫酸アンモニウム等の錯塩があり、
各種ホウフツ化銅のアミン錯塩としては、上記
の各種ホウフツ化銅と第一級アミン、第二級アミ
ン、第三級アミン、ジアミン、トリアミン、ポリ
アミン、尿素、アミン誘導体との錯塩がある。
上記の中工業的に重要なものは、テトラホウ酸
第２銅、メタホウ酸第２銅（一般にいうホウ酸
銅）、ホウフツ化第２銅並びにこれらとホウ酸ナ
トリウム、ホウ酸アンモニウム、アンモニア、尿
素、トリエチルアミン、ピリジン等との組成物で
ある。
又、前記した銅の含ホウ素酸塩組成物粉末は、
通常銅１重量部に対してホウ素が0.1〜1.0重量部
程度の組成比からなるものがよいが、場合によつ
ては助剤としてのフイラーを添加、混入して使用
することがあり、このフイラーとしては、燐酸ホ
ウ素、燐酸ナトリウム、燐酸カリウム、燐酸アン
チモン、ホウ酸ナトリウム、ホウ酸鉛、ホウ酸亜
鉛、フツ化鉛、五酸化バナジウム、タングステン
酸、無水ホウ酸、酸化珪素、酸化鉛、酸化チタ
ン、二酸化亜鉛、酸化アルミニウム、酸化マンガ
ン、酸化鉄、酸化コバルト、酸化ニツケル、酸化
希土類、酸化クロム、ピロリン酸バリウム、酸性
燐酸ジルコニウム、ホウ酸バナジウム、ピロリン
酸アルミニウム、ピロリン酸マグネシウム、酸性
燐酸マンガン、珪酸アルミニウムアルカリ、珪酸
ナトリウム、硫酸ナトリウム、各種珪酸塩の中か
ら選択されたものを適量混入せしめて使用すれば
よい。このフイラーは、銅の含ホウ素酸塩に対し
１％〜300％の範囲で使用することができる。
次に上記銅の含ホウ素酸塩組物粉末をインク化
してステイニング剤を得る工程について説明する
と、先ず上記銅の含ホウ素酸塩組成物粉末（第三
物質と共に）を、樹脂バインダー例えば、塩化ビ
ニル樹脂、醋酸ビニル樹脂、アクリル樹脂、繊維
素樹脂、エポキシ系樹脂、ウレタン系樹脂、不飽
和ポリエステル樹脂等の熱可塑性樹脂又は熱硬化
性樹脂を溶剤例えば、炭化水素類、エーテル類、
ケトン類、エステル類、アルコール類その他の単
独又はそれらの混合物に溶解せしめた樹脂溶液或
いは樹脂分散液に加え、必要により分散剤、例え
ばアミン系分散剤、脂肪酸系分散剤、界面活性剤
型分散剤、高分子型分散剤等や或いは場合によつ
ては増量剤等を加えてこれらを共にボールミル或
いはアトライター等により混練して均一に混合す
る。ここで得られるインキは各混合成分の配合比
や混合条件、添加物等の種類によつて通常の印刷
インキ状物から、塗料状物、ペースト状物、クリ
ーム状物、泥状物、懸濁状物等の各種の形態のも
のになすことができ、各種の使用方法に巾広く適
応したステイニング剤になし得る。
本発明において上記含ホウ素酸塩組成物粉末中
の銅とホウ素の含有比率を、銅１重量部に対して
ホウ素0.1〜1.0重量部とするのは、銅１重量部対
してホウ素が0.1重量部以下になるときは、銅イ
オンの移行を促進させるための媒体としてのホウ
素が不足となり、その結果銅イオンのガラス表面
層への導入が低下して充分な着色が得られなくな
るためである。
又一方ホウ素が銅１重量部に対し1.0重量部以
上になると、焼成時ホウ素化合物の皮膜が厚くな
つて銅イオンのガラス表面層への移行が逆に妨げ
られ着色効率が低下するためである。従つて銅と
ホウ素の含有比率は上記比率にする必要があり、
好ましくは銅１重量部に対してホウ素を0.4〜0.6
重量部なる含有比率のものがよい。
このインク化したところのステイニング剤を以
つてガラスを着色する例を示すと、先ず該インキ
状ステイニング剤を着色すべきガラスの表面に、
全面又は所望する図柄に塗布又は印刷して、ガラ
スの表面にステイニング剤の皮膜を形成する。ま
た、ステイニング剤をガラス表面に塗装する場合
であればガラスの表面にステイニング剤であるイ
ンキまたは塗料を吹付け、又はコートした後乾燥
して塗膜を設けるか、或いは上記インキまたは塗
料中にガラスを浸漬し、引上げ乾燥して塗膜を設
ければよく、又印刷の場合であれば、ガラスの表
面が平面のものであるときはスクリーン印刷法、
グラビヤオフセツト印刷法、平版オフセツト印刷
法等によればよく、又ガラス表面が曲面を有する
ものであるときには、凸凹版からタコ印刷用のパ
ツドの表面にインキを移し取つた後、更にこのパ
ツドからガラス表面に再移転印刷する所謂パツド
印刷法等を採用し立体曲面に図柄を印刷すること
ができる。
ここで得られるステイニング剤の皮膜は、マス
キングによる塗装や、吹付量の調整・変化、或い
は印刷版の版面積、深度、図柄等を変化させるこ
とによつて、任意の図柄のもの、或いは濃淡部分
を有するもの、図柄と濃淡を組合せてなるもの、
ぼかし調のもの等多くの態様のものに対し得るこ
とが可能である。
このようなステイニング剤の塗布又は印刷によ
つてガラス表面上にその皮膜を形成する方法とは
別の異なつた形成方法として所謂転写シートを用
いて行う転写方法が可能である。この転写方法の
場合について説明すると、例えばポリエステルフ
イルム、ポリプロピレンフイルム、ナイロンフイ
ルム、ポリエチレンフイルム、セロハン、紙、金
属箔等からなる基体シートに離型処理又は剥離層
を施し、その上に前記ステイニング剤であるイン
キで以つて印刷してステイニング剤の印刷皮膜層
を設ける。この皮膜層の印刷には各種の印刷法が
適用でき、前記同様に任意の図柄を有するもの、
或いは濃淡部分を有するもの、図柄と濃淡を組合
せたもの、ぼかし調のもの等が可能であることは
勿論であり、例えば連続的な濃度勾配を有するも
のや繊細華麗な図柄のものを得るにはグラビヤ印
刷法による網点グラビヤ版、コンベ版等を用いて
印刷すればよい。
このようにして形成された印刷皮膜層はガラス
に対して仮着可能な程度に接着性を有するもの、
或いは接着性を有しないものがあるが、前者の場
合にはステイニング剤の樹脂バインダーにあらか
じめ感熱接着性又は感圧接着性を有するものを使
用しておけばよい。又後者の場合には上記転写シ
ートのステイニング剤の印刷皮膜層の上に、ガラ
スに接着可能な接着剤層を設けた層構成にしてお
けばよい。
上記感熱接着性を有する樹脂バインダーとして
は、メチルメタクリレート樹脂を例にとれば、こ
れにロジン変性マレイン酸樹脂、石油樹脂、ノル
ボルネン樹脂、スチレン系樹脂、クマロンインデ
ン樹脂、その他のオリゴマー等が有利に混合され
使用できる。
又感圧接着性を有する樹脂バインダーとして
は、メチルメタクリレート樹脂を例にとれば、可
塑剤、オリゴマー等が有利に混合され使用でき
る。
又上記接着剤層にはポリアマイド系樹脂、ケト
ン樹脂、ゴム類、ビニールブチラール樹脂、ビニ
ールエーテル樹脂、バルサム類、各種オリゴマー
（熱硬化性オリゴマーを含む）等をも使用すると
よい。
次いでこのようにして得られた転写シートをガ
ラス表面に設置し、加熱または／および加圧して
転写シート上のステイニング剤の印刷皮膜層をガ
ラスの表面へ移行させる。この転写工程において
は通常の転写装置、例えばアツプダウン方式のも
の、ロール転写方式のもの等が使用でき、その転
写条件としては例えばロール転写機を使用する場
合には、ロールの表面温度を150℃〜230℃、転写
速度（ロールの周速度）を１秒間に５cm〜10cm程
度で行えばよい。
又この転写工程においては、ガラス表面へのス
テイニング剤の皮膜層の接着性を高めるために、
転写に先だつてガラスをプレヒートするのもよ
い。
更に又、上記加熱、加圧による転写方法とは異
なり、水溶性又は親水性のフイルムを使用してガ
ラス表面にステイニング剤の皮膜層を形成する方
法も適用できる。
この方法の場合について説明すると、例えば、
ポリビニルアルコール、ポリアクリルアミド、カ
ルボキシルメチル繊維素、ヒロドキシエチル繊維
素、メチル繊維素、ポリビニルピロリドン、ヒロ
ドキシルプロピル繊維素、カラギーナン、植物粘
液質、グルコマンナン、澱粉等の水溶性又は親水
性の物質を主とするフイルム上に、前記ガラス着
色用のステイニング剤のインキでもつて印刷して
該ステイニング剤の印刷皮膜層を設ける。これら
の印刷皮膜層は前記転写シートの場合と同様に各
種の繊細な図柄や濃度変化や濃度勾配を有するも
の、連続階調図柄を有するもの等が得られるのは
勿論である。次にこれらの使用法の一例を示すと
例えば、水溶性フイルムを前記印刷皮膜層が上に
なるようにして水面に浮かべる。ここで使用する
水は通常、常温でもよいが、例えば水溶性フイル
ムの溶解速度を速めたい場合には温湯を用いても
よい。この水水面に浮かんだフイルムの上から着
色すべきガラス物体を上記印刷皮膜層面に押圧し
ながら水面下に沈降させ、印刷皮膜層を単独又は
水溶性フイルムと共にガラス表面に仮着せしめ乍
ら水中から引上げて乾燥してガラス表面にステイ
ニング剤の皮膜層が形成される。
前記した皮膜層を単独で水面下よりガラス物体
の表面には仮着させるには、印刷皮膜層を設けた
水溶性フイルムを水面に浮かべ、該水溶性フイル
ムが溶解して皮膜のみが浮かんでいる状態になつ
た時点でガラス物体ですくい上げるようにすれば
よい。又皮膜のガラス物体への貼着力を特に必要
とする場合には、水面に浮かんだ印刷皮膜層面に
ガラス物体を接触させるに先だつて、印刷皮膜層
面に該皮膜層のガラスへの接着性を付与するため
に、該皮膜層表面を軟化させる溶剤或いは接着剤
等を吹付けるのがよい。この場合皮膜層面に塗布
した溶剤或いは接着剤が完全に乾燥し終えない間
にガラス物体を接触せしめる必要がある。勿論こ
のような使用法の他に適宜作業効率の上昇できる
方法があるときにはそれを採用しうることは当然
である。
以上の種々の形成方法によつてガラス表面上に
形成されたこれらのステイニング剤の皮膜からガ
ラスの表面に永久的な着色像を得るためには加熱
焼成が行われる。この加熱焼成はガラスの種類、
加熱環境にもよるが400℃〜800℃で達成される。
この焼成の雰囲気は、着色すべきガラスの種類に
よつて異なり、例えばガラスがその表面部分中に
錫イオン等の還元性物質を有するものであれば非
還元性の雰囲気、即ち通常の空気中で焼成すれば
よく、又上記還元性物質を有しないガラスの場合
であれば、水素ガス、一酸化炭素、都市ガス等の
還元性雰囲気下で焼成すればよい。焼成温度が
400℃以下であるときはステイニング剤の皮膜中
の銅の含ホウ素酸塩の熱分解が充分に行われず、
従つてガラス表面層中に銅分を充分に導入させる
ことができないので銅の有効使用率が低下し、発
色が充分に得られないほかステイニング剤の皮膜
中の有機物の熱分解による炭素分の付着が多くな
つて美しい着色効果が得られなくなる。又焼成温
度が800℃以上では銅の含ホウ素酸塩が急激に分
解するとか或いはその分解物が溶融してガラス表
面上を移動し着色のムラを生じたり、更にはガラ
ス自体が軟化して変形したり肌あれ等を生ずるの
で好ましくない。このような観点から本発明の方
法による加熱焼成（焼付ともいう）は400℃〜800
℃、望ましくは550℃〜750℃の加熱焼成が適して
いる。加熱焼成時間はガラスの軟化変形が著しく
ならない範囲に設定されるのは勿論である。
更に前記ステイニング剤による着色後のガラス
表面での該ステイニング剤の耐物性、或いは電気
伝導性、透電率等を改良する必要がある場合に
は、ステイニング剤を施すに先だつてガラスの表
面にあらかじめ金属酸化物薄層を形成しておき、
この上からステイニング剤を施して着色すればよ
い。この金属酸化物薄層の材料としては、例えば
酸化鉛、酸化インジウム、酸化錫、酸化亜鉛、酸
化チタン、酸化アルミニウム、酸化アンチモン等
が使用でき、該金属酸化物薄層をガラスの表面に
形成するには、例えば熔融したガラスを酸化雰囲
気中で熔融金属と接触させて形成するか、或いは
直接ガラスの表面に上記金属の化合物を含有する
インキを塗布、乾燥、焼成するか、更には真空蒸
着、スパツターリングや化学的、電気化学的方法
等によつて形成すればよい。
以上のようにしてステイニング剤によつて着色
されたガラスが得られるが、得られたガラスの表
面になおステイニング剤の焼成残渣がある場合に
は、塩酸、硝酸、硫酸、醋酸等を添加してなる酸
性の水に浸漬し、或いは水洗してこれらの残渣を
洗浄除去する。
本発明は以上のような構成よりなるので、ステ
イニング剤においては、従来の銅ステイニング法
に使用されているステイニング剤に比較して同一
の銅含有量でもつて極めて着色濃度の高いものが
得られ、特に最適のフイラーを助剤として混入せ
しめたときは更に一段と高着色効率を発揮できる
ものとなり、且つ焼成後表面残存物の除去が容易
となるほかガラス表面の光沢を低下せしめない。
又銅の含ホウ素酸塩自体の化学的安定性によ
り、ステイニング剤のインキとしての安定性が優
れているのでステイニング剤の長期保存が可能と
なり、常に色彩の鮮やかな赤色に着色できる好適
なステイニング剤であり、又着色方法においても
濃淡部分や連続階調図柄が容易に表現できる。特
に転写シートを用いる場合には更に一段と繊細華
麗な図柄のものや均一もしくは階調の濃度のもの
が得られるほか、ガラス表面へのステイニング剤
の皮膜形成工程が簡便迅速に行えるので量産性に
優れ且つ経済的である。又水溶性フイルムを使用
して前記皮膜を形成する場合には、薄い皮膜や溶
解状態の水溶性フイルムの柔軟性によつて、表面
が曲面或いは凹凸面からなる立体ガラス製品への
皮膜形成が容易となつて各種の立体形状のガラス
製品の着色が可能となるところの好適なガラスの
着色方法である。
次に本発明の実施例について説明する。以下に
示す実施例は多数の実験例中より本発明の技術的
内容をより詳しく解説するために抽出した代表例
であつて、本発明の内容は以下に示された実施例
のみに限定して解釈されるべきではなく、本発明
の主旨と精神とを逸脱せざる限り、任意にその実
施態様を変更して実施しうることは当然である。
本発明の優秀性は以下の実施例によつて益々明ら
かになるであろう。
実施例 １
銅の含ホウ素酸塩組成物粉末としてテトラホウ
酸第２銅〔CuB4O7〕の粉末（平均粒径5μ以下の
もの）100部と、これに樹脂バインダーとしてエ
チルメタクリレート樹脂100部、溶剤としてトル
エン100部とを加え、更にジアミン系分散剤１部
を加えて配合し、これをボールミルで24時間混練
しグラビヤインキ化したガラス着色用のステイニ
ング剤を得た。
又、テトラホウ酸第２銅の代わりにテトラホウ
酸第１銅、メタホウ酸第１銅、メタホウ酸第２銅
を使用しても銅含有率を一定にすれば同様にグラ
ビヤインキ化した場合、ほぼ同様な効果を有する
ガラス着色用ステイニング剤が得られた。
なお上記１部というのは１重量部のことを意味
するものであり、以下の実施例においても同様で
ある。
実施例 ２
銅の含ホウ素酸塩組成物粉末としてメタホウ酸
第２銅トリエチルアミン錯塩〔Cu（BO2）2・２
（C2H5）3N〕の粉末（平均粒径5μ以下のもの）
100部と、これに樹脂バインダーとしてメチルメ
タクリレート系樹脂50部、ロジン変性マレイン酸
樹脂50部、溶剤としてトルエン60部、エチルアル
コール40部を加え、更に分散剤〔商品名；デユオ
ミン（ライオンアクゾー株式会社製）〕１部を加
えて配合し、これをアルミナボール入のペイント
シエカーで36時間混練し、グラビヤインキ化した
ガラス着色用ステイニング剤を得た。
なお、メタホウ酸第２銅トリエチルアミン錯塩
の代わりにメタホウ酸第２銅アンモニヤ錯塩、メ
タホウ酸第２銅ピリジン錯塩、メタホウ酸第２銅
−ホウ酸ナトリウム複塩、−含水複塩、メタホウ
酸第２銅と硫酸ナトリウムの混合物を使用しても
銅含有率を一定にすれば、同様にグラビヤインキ
化した場合、ほぼ同様な効果を有するガラス着色
用ステイニング剤が得られた。
実施例 ３
銅の含ホウ素酸塩組成物粉末としてホウフツ化
第２銅ピリジン錯塩〔Cu（BF4）2・4C5H5N〕の
粉末100部を使用し、それ以外の配合物は実施例
１と同様のものを使用し且つ同様の配合と混練に
よつて同様にグラビヤインキ化したガラス着色用
ステイニング剤を得た。
実施例 ４
銅の含ホウ素酸塩組成物粉末として、ホウフツ
化第２銅アンモニヤ錯塩〔Cu（BF4）2・6NH3〕
の粉末100部を使用し、それ以外の配合物は実施
例３と同様のものを使用し、且つ同様の配合と混
練によつてグラビヤインキ化したガラス着色用ス
テイニング剤を得た。
実施例 ５
銅の含ホウ素酸塩組成物粉末として、過ホウ酸
銅〔Cu（BO3）2〕の粉末（平均粒度5μ以下のも
の）50部と燐酸ホウ素50部と、樹脂バインダーと
してブチルメタクリレート樹脂80部、醋酸ビニル
系樹脂20部と、溶剤として混合エステル系シンナ
ー90部を加え、それにジアミン系分散剤１部を加
えて配合し、ボールミルで48時間混練しグラビヤ
インキ化したガラス着色用ステイニング剤を得
た。
実施例 ６
実施例５のインキの配合物において燐酸ホウ素
の代わりにフイラーであるタングステン酸を50部
配合し、他は同様の配合物と配合比にし、それに
フイラーとしての酸化チタンの粉末を新たに50部
加えて擂潰機により60時間混練してペースト状化
したガラス着色用ステイニング剤を得た。
実施例 ７
銅の含ホウ素酸塩組成物粉末として、テトラホ
ウ酸第２銅〔CuB4O7〕の粉末50部と、ホウフツ
化第２銅〔Cu（BF4）2・4H2O〕の粉末50部との混
合物を用い、以後実施例１と同様の混合比にて配
合し、同様に混練してグラビヤインキ化したガラ
ス着色用ステイニング剤を得た。
実施例 ８
銅の含ホウ素酸塩組成物粉末として、テトラホ
ウ酸第２銅〔CuB4O7〕の粉末25部と、ホウフツ
化第２銅アンモニヤ錯塩〔Cu（BF4）2・4NH3〕
の粉末25部と、燐酸ビスマス50部との混合物を用
い、これに樹脂バインダーとしてビニールエチル
エーテル樹脂100部、溶剤としてトルエン・ジオ
キサン混合溶液100部、分散剤としてイオネツト
S85（三洋化成工業株式会社製）を１部加えて配
合し、以下実施例１と同様にしてグラビヤインキ
化したガラス着色用ステイニング剤を得た。
実施例 ９
実施例８のインキの配合物において燐酸ビスマ
スの代わりにフイラーである酸化鉛を同量配合し
て同様にしてグラビヤインキ化したガラス着色用
ステイニング剤を得た。
実施例 10
実施例８で得た配合インキに、フイラーである
珪酸マグネシウム25部加えて配合し以下実施例８
と同様にしてグラビヤインキ化したガラス着色用
ステイニング剤を得た。
実施例 11
実施例１で得たステイニング剤のインキを、厚
さ３mmの板ガラス面に、湿時塗布量24μのバーコ
ーターにて直接塗布し乾燥してステイニング剤の
皮膜を形成し、これを電気炉中に入れ都市ガスに
よる還元性雰囲気中で650℃で３分間加熱焼成し
た後、徐冷後炉内から取出し、200℃にまで下が
つた時点でその温度で再び熱風乾燥炉内において
２分間維持し、続いて室温にまで徐冷し、而る後
この板ガラスを硝酸1/20規定水溶液に１分間浸漬
後水洗いし板ガラス表面に残存するステイニング
剤層の焼成残渣を洗浄除去して赤色に着色された
透明板ガラスを得た。
次いでテトラホウ酸銅と同様にして従来より市
販の硫化銅、硫酸銅を使用してグラビヤインキ化
したステイニング剤を作成し、これを同一条件で
着色効果の測定を行つたところ次表のような結果
を得た。
The present invention relates to a novel invention relating to a staining method, which is a method for producing colored glass using metal colloids, and particularly to a staining agent containing copper, boron, etc., and a method for coloring glass using the staining agent. The staining method, which is a method of coloring glass, involves applying a solution of copper or silver compound, a mixture of these solutions and kaolin, etc., or a mixture of copper or silver compound and resin, etc. to the surface of the glass, and then heating it. This is a well-known method of coloring only the surface layer of glass by exchanging alkali ions with copper or silver ions in the surface layer of the glass, and then reducing it in an atmosphere containing hydrogen. Those using silver, silver nitrate, silver chloride, etc.) are called the silver staining method and are colored yellow, and those using copper compounds (copper sulfate, copper sulfide, etc.) are called the copper staining method and are colored red. It is well known that The use of precious metal compounds such as gold compounds or silver compounds in the staining agent used in this staining method has become extremely expensive due to the recent abnormal rise in the price of precious metals, making it difficult to put it to practical use. There's a problem. Therefore, the present inventors focused on the above-mentioned copper staining method, which is highly practical in terms of cost, and worked to put it into practical use. However, in conventional copper staining agents, copper compounds used as colorants, such as There are copper sulfide, copper chloride, copper sulfate, etc., but in view of the current situation where sufficient color development has not yet been obtained with these known products, as a result of various studies on improving these copper staining methods and copper staining agents,
If a copper borate composition powder is used as a coloring agent in a staining agent and this is used as an ink, the boron or boron compound in the staining agent will be used as an ink during the coloring process on the glass surface. They discovered that the present invention can be used as a medium to promote the transfer of copper ions introduced into the glass surface from the coloring agent, and also found that the efficiency of coloring glass can be significantly increased.The present invention was finally completed. That is, the present invention adds a filler if necessary to a copper borate composition powder, adds a resin binder, a solvent, and a dispersant if necessary,
This staining agent for glass coloring is characterized by being kneaded to form an ink, and the staining agent for glass coloring has a composition of 0.1 to 1.0 parts by weight of boron per 1 part by weight of copper. A coating layer of the staining agent is formed by coating or printing the boron-containing composition powder on the entire surface of the glass to be colored or in an arbitrary pattern, and then heating at 400°C to 800°C. The present invention relates to a method for coloring glass, which is characterized by introducing copper in a coating layer of a staining agent into the surface layer of the glass and coloring the glass by heating and firing the staining agent. In addition to the above-mentioned coating and printing methods, the process of applying the staining agent to the surface may include a method of applying a transfer image to the glass surface by heating and pressing using a transfer sheet on which a printed film layer of the staining agent has been formed, or a method of applying a printed film of the staining agent to the glass surface. It also includes a method in which a layered water-soluble film is floated on the surface of water, and a glass object to be colored is pressed from above and allowed to settle to temporarily adhere. The copper borate composition powder in the present invention includes copper borate compound powders, such as various copper borates, various alkali complex salts of copper borate, ammonia complex salts, amine complex salts, etc., or copper borofluoride compound powders. For example, powders of various copper borofluorides, alkali complex salts of various copper borofluorides, ammonia complex salts, amine complex salts, etc., as well as mixtures of the above-mentioned copper borate compound powders and the above-mentioned copper borofluoride compound powders, etc. can be arbitrarily used. Examples of the various copper borates mentioned above include cuprous tetraborate, cupric tetraborate, and cuprous metaborate.
Copper, cupric metaborate, cupric perborate, etc. can be used alone or in mixtures of two or more, and various copper borate alkali salts include the above-mentioned various copper borates, sodium borate, potassium borate, Or complex salts with lithium borate, etc. Examples of various ammonia complex salts of copper borate include the above-mentioned various copper borate and ammonia, ammonium halides, ammonium borate, ammonium carbonate,
There are complex salts such as ammonium sulfate, and various amine salts of copper borate include the above-mentioned copper borate and primary amines, secondary amines, tertiary amines, diamines, triamines, polyamines, urea, and amine derivatives. There are complex salts, double salts, etc. of various copper borofluorides, such as cuprous tetrafluoroborate, cupric tetrafluoroborate, cuprous oxytrifluoroborate, cuprous sulfatooxyborate , cupric dihydroxydifluoroborate, etc. Examples of various alkali complex salts of copper borofluoride include complex salts of the various copper borofluorides mentioned above and sodium borate, potassium borate, or lithium borate. As an ammonia complex salt of copper borofluoride,
There are complex salts of the above-mentioned copper borofluorides and ammonia, ammonium halides, ammonium borate, ammonium carbonate, ammonium sulfate, etc.; There are complex salts with secondary amines, tertiary amines, diamines, triamines, polyamines, urea, and amine derivatives. The above-mentioned materials that are important in the medium industry include cupric tetraborate, cupric metaborate (commonly referred to as copper borate), cupric borate, and these together with sodium borate, ammonium borate, ammonia, urea, It is a composition with triethylamine, pyridine, etc. In addition, the copper borate composition powder described above is
Usually, it is good to have a composition ratio of about 0.1 to 1.0 parts by weight of boron per 1 part by weight of copper, but in some cases filler may be added or mixed as an auxiliary agent, and this filler Examples include boron phosphate, sodium phosphate, potassium phosphate, antimony phosphate, sodium borate, lead borate, zinc borate, lead fluoride, vanadium pentoxide, tungstic acid, boric anhydride, silicon oxide, lead oxide, titanium oxide. , zinc dioxide, aluminum oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, rare earth oxide, chromium oxide, barium pyrophosphate, zirconium acid phosphate, vanadium borate, aluminum pyrophosphate, magnesium pyrophosphate, manganese acid phosphate, silicic acid An appropriate amount of one selected from aluminum alkali, sodium silicate, sodium sulfate, and various silicates may be mixed in and used. This filler can be used in a range of 1% to 300% based on the copper borate. Next, to explain the process of obtaining a staining agent by turning the copper borate composition powder into an ink, first, the copper borate composition powder (along with a third substance) is mixed with a resin binder such as chloride. Thermoplastic resins or thermosetting resins such as vinyl resins, vinyl acetate resins, acrylic resins, cellulose resins, epoxy resins, urethane resins, and unsaturated polyester resins are mixed with solvents such as hydrocarbons, ethers,
In addition to the resin solution or resin dispersion dissolved in ketones, esters, alcohols, etc. alone or in mixtures thereof, if necessary, a dispersant such as an amine dispersant, a fatty acid dispersant, a surfactant type dispersant , a polymer type dispersant, etc., or an extender, etc. as the case may be, and these are kneaded together using a ball mill, an attritor, etc., and mixed uniformly. The ink obtained here varies from ordinary printing ink to paint, paste, cream, slurry, suspension, etc., depending on the blending ratio of each mixed component, mixing conditions, and types of additives. It can be made into various forms such as shaped articles, and can be made into staining agents that are widely adapted to various usage methods. In the present invention, the content ratio of copper and boron in the above-mentioned boron-containing salt composition powder is 0.1 to 1.0 parts by weight per 1 part by weight of copper, which means that 0.1 parts by weight of boron per 1 part by weight of copper. If it is below, there will be a shortage of boron as a medium for promoting the transfer of copper ions, and as a result, the introduction of copper ions into the glass surface layer will decrease, making it impossible to obtain sufficient coloring. On the other hand, if the amount of boron exceeds 1.0 parts by weight per 1 part by weight of copper, the film of the boron compound becomes thick during firing, and the transfer of copper ions to the glass surface layer is hindered, resulting in a decrease in coloring efficiency. Therefore, the content ratio of copper and boron needs to be the above ratio,
Preferably 0.4 to 0.6 boron per 1 part by weight of copper.
A content ratio of parts by weight is preferable. To show an example of coloring glass using this ink-formed staining agent, first, the ink-like staining agent is applied to the surface of the glass to be colored.
A staining agent film is formed on the surface of the glass by coating or printing on the entire surface or a desired pattern. In addition, if a staining agent is to be applied to the glass surface, the ink or paint that is the staining agent is sprayed or coated on the glass surface and then dried to form a coating, or the ink or paint used in the above-mentioned ink or paint is applied. The coating film can be formed by dipping the glass in water, pulling it up and drying it, or in the case of printing, if the surface of the glass is flat, screen printing,
The gravure offset printing method, the lithographic offset printing method, etc. may be used, and when the glass surface has a curved surface, after the ink is transferred from the relief plate to the surface of the pad for tacho printing, further from this pad. It is possible to print patterns on three-dimensional curved surfaces by employing the so-called pad printing method, which retransfer prints onto the glass surface. The staining agent film obtained here can be formed into any pattern or shade by painting by masking, adjusting/changing the spray amount, or changing the plate area, depth, pattern, etc. of the printing plate. Things that have parts, things that combine designs and shading,
It is possible to obtain many types of images such as blurred images. A transfer method using a so-called transfer sheet is possible as a different method of forming a film on the glass surface by applying or printing a staining agent. To explain the case of this transfer method, for example, a base sheet made of polyester film, polypropylene film, nylon film, polyethylene film, cellophane, paper, metal foil, etc. is subjected to a release treatment or a release layer is applied, and the staining agent is applied thereon. A printed film layer of the staining agent is provided by printing with an ink of the following. Various printing methods can be applied to printing this film layer, including those with arbitrary designs as described above,
Of course, it is also possible to create a pattern with light and dark areas, a combination of patterns and shading, and a blurred pattern. Printing may be performed using a halftone gravure plate, a conveyor plate, etc. using a gravure printing method. The printed film layer formed in this way has adhesiveness to the extent that it can be temporarily attached to glass;
Alternatively, some staining agents do not have adhesive properties, but in the former case, a resin binder with heat-sensitive adhesive properties or pressure-sensitive adhesive properties may be used in advance as the resin binder of the staining agent. In the latter case, an adhesive layer capable of adhering to glass may be provided on the staining agent printed film layer of the transfer sheet. As the resin binder having heat-sensitive adhesive properties, for example, methyl methacrylate resin is used, but in addition to this, rosin-modified maleic acid resin, petroleum resin, norbornene resin, styrene resin, coumaron indene resin, and other oligomers are advantageously used. Can be mixed and used. Further, as a resin binder having pressure-sensitive adhesive properties, for example, methyl methacrylate resin can be advantageously mixed with a plasticizer, an oligomer, and the like. In addition, polyamide resins, ketone resins, rubbers, vinyl butyral resins, vinyl ether resins, balsams, various oligomers (including thermosetting oligomers), etc. may also be used in the adhesive layer. The transfer sheet thus obtained is then placed on a glass surface and heated and/or pressurized to transfer the printed film layer of the staining agent on the transfer sheet to the glass surface. In this transfer process, a normal transfer device such as an up-down type or a roll transfer type can be used, and the transfer conditions include, for example, when using a roll transfer machine, the surface temperature of the roll is 150 ° C. The transfer may be carried out at 230° C. and at a transfer speed (circumferential speed of the roll) of about 5 cm to 10 cm per second. In addition, in this transfer process, in order to improve the adhesion of the staining agent film layer to the glass surface,
It is also a good idea to preheat the glass prior to transfer. Furthermore, unlike the above transfer method using heat and pressure, a method of forming a coating layer of a staining agent on the glass surface using a water-soluble or hydrophilic film can also be applied. To explain the case of this method, for example,
Mainly water-soluble or hydrophilic substances such as polyvinyl alcohol, polyacrylamide, carboxylmethyl cellulose, hydroxyethyl cellulose, methyl cellulose, polyvinylpyrrolidone, hydroxypropyl cellulose, carrageenan, plant mucilage, glucomannan, starch, etc. An ink of the staining agent for glass coloring is printed on the film to provide a printed film layer of the staining agent. Of course, these printed film layers can have various delicate designs, density changes, density gradients, continuous gradation patterns, etc., as in the case of the transfer sheet. Next, to give an example of how to use these, for example, a water-soluble film is floated on the water surface with the printed film layer facing upward. The water used here may normally be at room temperature, but if, for example, it is desired to accelerate the dissolution rate of the water-soluble film, hot water may be used. A glass object to be colored is pressed onto the surface of the printed film layer from above the film floating on the surface of the water, and is allowed to settle below the surface of the water. A coating layer of staining agent is formed on the glass surface by pulling it up and drying it. In order to temporarily attach the above-mentioned film layer alone to the surface of a glass object from below the water surface, a water-soluble film provided with a printed film layer is floated on the water surface, and the water-soluble film is dissolved and only the film remains floating. Once it reaches this state, you can scoop it up with a glass object. If adhesion of the film to the glass object is particularly required, the adhesion of the film layer to the glass may be imparted to the surface of the printed film layer before the glass object is brought into contact with the surface of the printed film layer floating on the water surface. In order to do this, it is preferable to spray a solvent or adhesive that softens the surface of the film layer. In this case, it is necessary to bring the glass object into contact with the glass object before the solvent or adhesive applied to the surface of the film layer has completely dried. Of course, if there is a method that can appropriately increase work efficiency in addition to this usage method, it is of course possible to adopt that method. In order to obtain a permanent colored image on the glass surface from the staining agent film formed on the glass surface by the various formation methods described above, heating and baking are performed. This heating and firing process is performed on the types of glass,
Depending on the heating environment, it is achieved between 400℃ and 800℃.
The firing atmosphere differs depending on the type of glass to be colored; for example, if the glass has reducing substances such as tin ions in its surface, it will be in a non-reducing atmosphere, that is, in normal air. If the glass does not contain the above-mentioned reducing substance, it may be fired in a reducing atmosphere such as hydrogen gas, carbon monoxide, city gas, etc. The firing temperature is
If the temperature is below 400℃, the thermal decomposition of the copper borate in the staining agent film will not take place sufficiently.
Therefore, it is not possible to introduce a sufficient amount of copper into the glass surface layer, so the effective usage rate of copper decreases, and sufficient color development cannot be obtained. If the amount of adhesion increases, it becomes impossible to obtain a beautiful coloring effect. In addition, if the firing temperature exceeds 800°C, the copper borate may rapidly decompose, or its decomposed products may melt and move on the glass surface, causing uneven coloring, or even the glass itself may become softened and deformed. This is not desirable as it may cause irritation or irritation of the skin. From this point of view, heating and firing (also called baking) according to the method of the present invention is carried out at temperatures between 400°C and 800°C.
C., preferably 550.degree. C. to 750.degree. C., is suitable for firing. Of course, the heating and firing time is set within a range that does not cause significant softening and deformation of the glass. Furthermore, if it is necessary to improve the physical resistance of the staining agent on the glass surface after it has been colored with the staining agent, or the electrical conductivity, the electrical conductivity, etc., it is necessary to improve the glass surface before applying the staining agent. A thin metal oxide layer is formed on the surface in advance,
You can color it by applying a staining agent over it. As the material for this metal oxide thin layer, for example, lead oxide, indium oxide, tin oxide, zinc oxide, titanium oxide, aluminum oxide, antimony oxide, etc. can be used, and the metal oxide thin layer is formed on the surface of the glass. For example, it is formed by bringing molten glass into contact with molten metal in an oxidizing atmosphere, or by directly applying an ink containing the above-mentioned metal compound onto the surface of the glass, drying, and baking, or by vacuum evaporation, It may be formed by sputtering, a chemical method, an electrochemical method, or the like. Glass colored with a staining agent is obtained as described above, but if there are still firing residues of the staining agent on the surface of the obtained glass, add hydrochloric acid, nitric acid, sulfuric acid, acetic acid, etc. These residues are removed by immersion in acidic water or washing with water. Since the present invention has the above configuration, the staining agent has an extremely high coloring density even with the same copper content compared to the staining agent used in the conventional copper staining method. In particular, when the most suitable filler is mixed as an auxiliary agent, even higher coloring efficiency can be exhibited, and the surface residue after firing is easily removed, and the gloss of the glass surface is not reduced. In addition, due to the chemical stability of the copper borate itself, the staining agent has excellent stability as an ink, making it possible to store the staining agent for a long time. It is a staining agent, and can also be used to easily create shading areas and continuous tone patterns. In particular, when a transfer sheet is used, it is possible to obtain even more delicate and gorgeous designs and uniform or gradation density, and the process of forming a film of staining agent on the glass surface can be carried out simply and quickly, which facilitates mass production. Excellent and economical. In addition, when forming the film using a water-soluble film, the film can be easily formed on three-dimensional glass products with curved or uneven surfaces due to the thin film or the flexibility of the water-soluble film in a dissolved state. This is a suitable glass coloring method that enables the coloring of glass products of various three-dimensional shapes. Next, examples of the present invention will be described. The examples shown below are representative examples extracted from a large number of experimental examples in order to explain the technical contents of the present invention in more detail, and the contents of the present invention are limited to the examples shown below. This invention should not be construed as such, and it goes without saying that the embodiments may be modified and implemented as desired without departing from the gist and spirit of the invention.
The superiority of the present invention will become more apparent from the following examples. Example 1 100 parts of cupric tetraborate (CuB 4 O 7 ) powder (with an average particle size of 5 μm or less) as a copper borate composition powder, 100 parts of ethyl methacrylate resin as a resin binder, 100 parts of toluene was added as a solvent, and 1 part of a diamine dispersant was added and blended, and the mixture was kneaded in a ball mill for 24 hours to obtain a staining agent for glass coloring, which was made into a gravure ink. Furthermore, even if cuprous tetraborate, cuprous metaborate, or cupric metaborate is used instead of cupric tetraborate, if the copper content is kept constant, the result will be almost the same when made into a gravure ink. A staining agent for glass coloring having excellent effects was obtained. Note that the above 1 part means 1 part by weight, and the same applies to the following examples. Example 2 Cupric triethylamine metaborate complex salt [Cu(BO 2 ) 2.2 ] as copper borate composition powder
(C 2 H 5 ) 3 N] powder (average particle size 5μ or less)
100 parts, 50 parts of methyl methacrylate resin as a resin binder, 50 parts of rosin-modified maleic acid resin, 60 parts of toluene and 40 parts of ethyl alcohol as a solvent, and a dispersant [trade name: Duomine (Lion Akzo Co., Ltd.) (manufactured by the company)] was added and mixed for 36 hours in a paint shaker containing alumina balls to obtain a staining agent for glass coloring made into gravure ink. In addition, cupric metaborate ammonia complex salt, cupric metaborate pyridine complex salt, cupric metaborate-sodium borate double salt, -hydrous double salt, cupric metaborate, instead of cupric metaborate triethylamine complex salt. Even if a mixture of 1 and sodium sulfate was used and the copper content was kept constant, a staining agent for glass coloring having almost the same effect was obtained when made into a gravure ink. Example 3 100 parts of powder of cupric pyridine borofluoride [Cu(BF 4 ) 2.4C 5 H 5 N] was used as the copper borate composition powder, and the other formulations were as in Example. A staining agent for glass coloring, which was made into gravure ink in the same manner as in Example 1, was obtained by using the same compound and kneading as in Example 1. Example 4 Cupric ammonium borofluoride complex salt [Cu(BF 4 ) 2.6NH 3 ] as copper borate composition powder
A staining agent for glass coloring made into a gravure ink was obtained by using 100 parts of the powder, using the same formulation as in Example 3, and using the same formulation and kneading process. Example 5 As a copper borate composition powder, 50 parts of copper perborate [Cu(BO 3 ) 2 ] powder (average particle size of 5 μ or less), 50 parts of boron phosphate, and butyl methacrylate as a resin binder were used. Glass coloring stay made by adding 80 parts of resin, 20 parts of vinyl acetate resin, 90 parts of mixed ester thinner as a solvent, and 1 part of diamine dispersant, and kneading the mixture in a ball mill for 48 hours to make gravure ink. A coating agent was obtained. Example 6 In the ink formulation of Example 5, 50 parts of tungstic acid, which is a filler, was added instead of boron phosphate, and the other proportions were the same as those of the same formulation, and titanium oxide powder was newly added as a filler. 50 parts were added and kneaded for 60 hours using a crusher to obtain a paste-like staining agent for glass coloring. Example 7 As a copper borate composition powder, 50 parts of cupric tetraborate [CuB 4 O 7 ] powder and cupric borofluoride [Cu(BF 4 ) 2.4H 2 O] powder were used. Using a mixture with 50 parts, the mixture was blended at the same mixing ratio as in Example 1, and kneaded in the same manner as in Example 1 to obtain a staining agent for glass coloring, which was made into a gravure ink. Example 8 As a copper borate composition powder, 25 parts of powder of cupric tetraborate [CuB 4 O 7 ] and cupric ammonium borofluoride complex salt [Cu(BF 4 ) 2.4NH 3 ] were used.
A mixture of 25 parts of powder and 50 parts of bismuth phosphate was used, along with 100 parts of vinyl ethyl ether resin as a resin binder, 100 parts of a toluene/dioxane mixed solution as a solvent, and ionets as a dispersant.
One part of S85 (manufactured by Sanyo Chemical Industries, Ltd.) was added and blended, and the same procedure as in Example 1 was carried out to obtain a staining agent for glass coloring, which was made into a gravure ink. Example 9 A staining agent for glass coloring, which was made into a gravure ink, was obtained in the same manner as in Example 8 except that the same amount of lead oxide as a filler was added in place of bismuth phosphate in the ink formulation of Example 8. Example 10 25 parts of magnesium silicate as a filler was added to the blended ink obtained in Example 8, and the following Example 8 was prepared.
A glass coloring staining agent made into gravure ink was obtained in the same manner as above. Example 11 The staining agent ink obtained in Example 1 was applied directly to a 3 mm thick plate glass surface using a bar coater with a wet coating amount of 24μ, and dried to form a staining agent film. was placed in an electric furnace and heated and fired at 650℃ for 3 minutes in a reducing atmosphere using city gas, then taken out from the furnace after slow cooling, and when the temperature had dropped to 200℃, it was placed in the hot air drying oven again at that temperature. The plate glass was maintained for 2 minutes, then slowly cooled to room temperature, and then the plate glass was immersed in a 1/20N nitric acid aqueous solution for 1 minute and then washed with water to remove the firing residue of the staining agent layer remaining on the plate glass surface. A transparent plate glass colored red was obtained. Next, in the same manner as copper tetraborate, a gravure ink staining agent was prepared using commercially available copper sulfide and copper sulfate, and the coloring effect was measured under the same conditions. Got the results.
【表】
実施例 12
実施例５で得たステイニング剤のインキを、そ
の表面層に錫イオンからなる還元性物質が分散さ
れてなる厚さ５mmの強化板ガラス面に、スクリー
ン印刷により２回重ね刷りしてステイニング剤の
厚さ5μの皮膜を形成し、これを予め600℃まで加
熱昇温させた電気炉中に入れ３分間加熱焼成し、
徐冷後炉内から取出し、200℃にまで降温させた
時点でその温度で熱風乾燥炉内において２分間維
持し、続いて室温にまで徐冷した後、この板ガラ
スを硝酸の1/10の規定水溶液に３秒間浸漬後水洗
し板ガラス表面に残存するステイニング剤層の焼
成残渣を洗浄除去して赤紅色に着色された透明強
化板ガラスを得た。
尚、ガラスの表面層に錫イオンを注入分散させ
るには通常の方法、即ち加熱されたガラスの表面
を熔融金属（錫）溶面に接触させて注入させる方
法によればよい。
実施例 13
実施例３で得たステイニング剤のインキを、そ
の表面層に錫イオンからなる還元性物質が分散せ
しめられた厚さ３mmの透明板ガラス面に、スプレ
ーによる吹付法によつて、帯状の図柄で且つ片側
がぼかし調であるステイニング剤の皮膜を形成さ
せ、以下実施例12と同様に加熱焼成工程、冷却工
程、焼成残渣除去を行つて片側がぼかし調の図柄
を有する赤色に着色された透明板ガラスを得た。
実施例 14
実施例４で得たステイニング剤のインキを、そ
の表面層内に錫イオンからなる還元性物質が分散
され且つ表面層上に金属酸化物薄層である酸化ア
ルミニウムの薄層が形成された厚さ４mmの板ガラ
スの表面に、スクリーン印刷により、部分的に重
ね刷りを３回行つて印刷皮膜の厚さに勾配を設け
た皮膜を形成し、これを予め650℃まで加熱昇温
させた電気炉中に入れ３分間加熱焼成し、以後実
施例12と同様に加熱焼成して室温にまで徐冷した
後、板ガラス表面に残存するステイニング剤層の
焼成残渣を同様にして洗浄除去して濃度勾配を有
する赤色に着色された透明板ガラスを得た。
実施例 15
メタホウ酸第２銅〔Cu（BO2）2〕の粉末40部
と、これに樹脂バインダーとして変性醋酸ビニー
ル系樹脂100部、溶剤としてメチルアルコールと
ブチルアルコールの混合比４：１のものを70部を
加え更にフイラーとして酸化チタニウム30部及び
二酸化マンガン20部とを加えて配合し、これを擂
潰機で24時間混練してステイニング剤のペースト
を作製した。次いでこのペーストを用いてパツド
印刷法により、ガラス壜の表面に、図柄を構成す
るステイニング剤の皮膜を形成し、これを電気炉
中に入れ都市ガスによる還元性雰囲気中で680℃
で３分間加熱焼成した。次にこれを徐冷後炉内か
ら取出し200℃にまで降温させた時点でその温度
で熱風乾器内で２分間維持し、続いて室温にまで
徐冷した後、塩酸の1/10規定水溶液に５秒間浸漬
後水洗しガラス壜の表面に残存するステイニング
剤層の焼成残渣を洗浄除去して赤色に着色された
ガラス壜を得た。この方法はガラスコツプにも同
じように適用できる。
実施例 16
実施例２で得たステイニング剤のインキに更に
トルエン及びエチルアルコールの混合溶剤を適量
加えて希釈し、岩田式粘度計にて20秒の粘度に調
節したインキを作製し、次いでこのインキを用い
てグラビヤコーターにより、アクリル樹脂組成物
のコーテイングによつて形成された剥離層を表面
に設けた厚さ25μのポリエステルフイルムの該剥
離層面上に、全面にコートしてステイニング剤の
厚さ3μの皮膜層を設けて転写シートを作製し、
次にこの転写シートを用いて加熱ロール式転写法
によつて表面層に環元性物質（錫化合物）が分散
された厚さ３mmの板ガラスの表面にステイニング
剤の転写皮膜を設け、ベースフイルム（ポリエス
テルフイルム）を転写面から剥離させた後、以後
実施例12と同様の加熱焼成工程、冷却工程、焼成
残渣除去工程にて処理することによつて全面均一
な濃度の赤色に着色された板ガラスを得た。
実施例 17
実施例１で得たステイニング剤のインキに更に
トルエンを適量加えて希釈し、岩田式粘度計にて
20秒の粘度に調節したインキを作製し、次いでこ
のインキを用いてグラビヤ多色印刷機により、ア
クリル樹脂組成物の印刷によつて形成された剥離
層を表面に設けた厚さ16μのポリエステルフイル
ムの該剥離層面上に、連続的に印刷濃度を変化さ
せたボカシ調の図柄を印刷してステイニング剤の
ボカシ図柄の印刷皮膜層を設け、更にこの上に同
じくグラビヤ印刷によりポリアミド系樹脂組成物
からなる感熱接着剤層を設けて転写シートを作製
し、次にこの転写シートを用いて加熱ロール式転
写法によつて厚さ５mmの板ガラスの表面にステイ
ニング剤の転写皮膜を設け、ポリエステルフイル
ムを転写面から剥離させた後以後実施例11と同様
の加熱焼成工程、冷冷却工程、焼成残渣除去工程
を行うことによつて赤色に着色された連続的な濃
度勾配によるぼかし調の図柄を有する板ガラスを
得た。
実施例 18
実施例７で得たステイニング剤のインキに更に
トルエンを適量加えて希釈し、岩田式粘度計にて
20秒の粘度に調節したインキを作製し、次いでこ
のインキを用いて、剥離層を設けた25μのポリエ
ステルフイルムの該剥離層（アクリル樹脂組成
物）の上に、グラビヤ多色印刷機によつて連続階
調図柄の印刷皮膜層を形成し、更にその上に同じ
くグラビヤ印刷によるポリアミド樹脂組成物から
なる感熱接着剤層を設けて転写シートを作製し
た。
次にこの転写シートを用いて、アルミナゲルを
コートしたガラス壜の該アルミナゲルコート面に
転写シートの転写層（剥離層、ステイニング剤の
印刷皮膜層、接着剤層等）を加熱転写して移行さ
せ、ポリエステルフイルムを転写面から剥離させ
た後、電気炉中にて550℃、20分間加熱し、徐冷
後炉内から取出し、而る後このガラス壜を硫酸の
１／２０規定水溶液に浸漬後水洗しガラス壜の表面に
残存するステイニング剤の焼成残渣を洗浄除去し
て赤色に着色された連続階調図柄を有するガラス
壜を得た。
又上記アルミナゲルコートの代わりにシリカゲ
ルをコートしたガラス壜の上に同様に転写絵付を
行つても赤色に着色された同様のガラス壜が得ら
れた。
実施例 19
実施例17で得た粘度調節されたインキを用いて
スプレイガンによる吹付によつてぼかし調の図柄
からなる塗装皮膜層並びに感熱接着剤層を設けた
転写シートを作製し、予め50℃に加熱された厚さ
５mmの板ガラスの表面に以後実施例17と同様に転
写工程、加熱焼成工程、冷却工程、焼成残渣除去
工程を行うことによつて赤色に着色されたぼかし
調の図柄を有する板ガラスを得た。
実施例 20
実施例10で得たステイニング剤のインキを用い
て、厚さ20μのポリビニルアルコールからなる水
溶性の基体シート面上に、グラビヤ印刷機によつ
て全面にステイニング剤の印刷皮膜層を設けて水
溶性の転写シートを作製した。次いでこの転写シ
ートを、ステイニング剤の印刷皮膜層が上方にな
るようにして用意された水槽の水面（常温の）に
浮かべ、下方の水溶性の基体シートが水に溶解し
て完全に除去されてステイニング剤の印刷皮膜層
のみとなつた段階で、該印刷皮膜層に上方からガ
ラス壜の底を下にして押付け、そのまま水面下に
沈降させることによつて水圧により印刷皮膜層を
ガラス壜の外面の底から上方へ均一に展着して沿
わせた後、該ガラス壜を水中から底を上に向けて
引上げると、ガラス壜の外表面にステイニング剤
の印刷皮膜層が均一に密着される。次にこれを乾
燥した後、実施例11と同様の加熱焼成工程、冷却
工程、焼成残渣除去工程等を行つた結果、均一な
赤色に着色されたガラス壜を得た。
又上記水溶性の基体シート上に設けるステイニ
ング剤のインキによる全面均一な印刷皮膜層の代
わりに、濃度勾配を有するぼかし調の図柄の印刷
皮膜層を設けたところの水溶性の転写シートを用
いて同様に処理しても赤色に着色されたぼかし調
の図柄を有するガラス壜が得られた。
更に又上記ガラス壜の代わりに厚さ３mmの板ガ
ラスを使用し同様に処理しても赤色に着色された
ぼかし図柄を有する板ガラスが得られた。
実施例 21
実施例９で得たステイニング剤のインキを用い
て厚さ30μのメチルセルローズからなる水溶性の
基体シート面上に、グラビヤ印刷機によつて全面
にステイニング剤の印刷皮膜層を設け更にその上
にポリアミド系樹脂組成物からなる接着剤層を設
けて水溶性の転写シートを作製した。次いでこの
転写シートを接着剤層が上方になるようにして用
意された水槽の水面（30℃）に浮かべ、下方の水
溶性の基体シートが50％以上溶解した時点で接着
剤層面へ上方から溶剤（トルエン／メチルアルコ
ール、１±１の混合溶剤）をスプレイガンによつ
て適量吹付けた後、該溶剤によつて溶解した接着
剤層が乾燥しない間に上方から、表面層に錫化合
物からなる還元性物質が注入分散された板ガラス
を押付け、そのまま水面下に沈降させることによ
つて水圧により印刷皮膜層を水溶性フイルムと共
に板ガラスの表面に均一に展着して沿わせた後、
該板ガラスを展着面を上に向けて水中から引上げ
ながら水溶性フイルムを完全に溶解除去する。次
にこれを乾燥した後、実施例12と同様の加熱焼成
工程、冷却工程、焼成残渣除去工程等を行つた結
果、全面均一に赤色に着色された板ガラスを得
た。
又上記水溶性基体シートの上に設けるステイニ
ング剤のインキによる全面均一な印刷皮膜層の代
わりに、濃度勾配を有するぼかし調の図柄の印刷
皮膜層を設けたところの水溶性の転写シートを用
いて同様に処理しても赤色に着色されたぼかし調
の図柄を有する板ガラスが得られた。[Table] Example 12 The ink of the staining agent obtained in Example 5 was overlaid twice by screen printing on the surface of a 5 mm thick tempered plate glass whose surface layer had a reducing substance made of tin ions dispersed therein. A 5μ thick film of staining agent is formed by printing, and this is placed in an electric furnace that has been heated to 600°C for 3 minutes.
After slow cooling, the plate glass is taken out from the furnace, and when the temperature is lowered to 200°C, it is maintained at that temperature in a hot air drying oven for 2 minutes, and then slowly cooled to room temperature. After being immersed in an aqueous solution for 3 seconds, the plate glass was washed with water to remove the firing residue of the staining agent layer remaining on the surface of the plate glass, thereby obtaining a reddish colored transparent reinforced plate glass. Incidentally, tin ions may be implanted and dispersed in the surface layer of the glass by a conventional method, that is, by bringing the surface of the heated glass into contact with the molten metal (tin) surface and implanting the tin ions. Example 13 The ink of the staining agent obtained in Example 3 was sprayed onto a 3 mm thick transparent plate glass surface in which a reducing substance consisting of tin ions was dispersed in the surface layer. A film of staining agent with a pattern of 1 and a shading pattern on one side is formed, and then a heating and firing process, a cooling process, and a firing residue removal are performed in the same manner as in Example 12, and one side is colored red with a pattern in a shading pattern. A transparent plate glass was obtained. Example 14 The staining agent ink obtained in Example 4 was prepared by dispersing a reducing substance consisting of tin ions in the surface layer and forming a thin layer of aluminum oxide, which is a thin metal oxide layer, on the surface layer. On the surface of the plate glass with a thickness of 4 mm, screen printing was performed to partially overprint three times to form a film with a gradient in the thickness of the printed film, and this was heated to 650 ° C in advance. After heating and baking in the same manner as in Example 12 and slowly cooling to room temperature, the baking residue of the staining agent layer remaining on the surface of the plate glass was washed and removed in the same manner. A transparent plate glass colored red with a concentration gradient was obtained. Example 15 40 parts of powder of cupric metaborate [Cu(BO 2 ) 2 ], 100 parts of modified vinyl acetate resin as a resin binder, and a mixture of methyl alcohol and butyl alcohol in a mixing ratio of 4:1 as a solvent. 70 parts of was added thereto, and 30 parts of titanium oxide and 20 parts of manganese dioxide as fillers were further added and blended, and this was kneaded for 24 hours using a crusher to prepare a paste of a staining agent. Next, this paste is used to form a staining agent film on the surface of the glass bottle that forms the design using the pad printing method, and this is placed in an electric furnace and heated at 680°C in a reducing atmosphere of city gas.
It was heated and baked for 3 minutes. Next, after slow cooling, this was taken out from the furnace and the temperature was lowered to 200°C. At that point, it was maintained at that temperature in a hot air dryer for 2 minutes, then slowly cooled to room temperature, and then a 1/10 N aqueous solution of hydrochloric acid was added. After being immersed in water for 5 seconds, the glass bottle was washed with water to remove the firing residue of the staining agent layer remaining on the surface of the glass bottle, thereby obtaining a red colored glass bottle. This method can be applied to glass tops as well. Example 16 The staining agent ink obtained in Example 2 was further diluted by adding an appropriate amount of a mixed solvent of toluene and ethyl alcohol to prepare an ink whose viscosity was adjusted to 20 seconds using an Iwata viscometer. Using an ink and a gravure coater, coat the entire surface of a 25μ thick polyester film with a release layer formed by coating an acrylic resin composition on the release layer surface to a thickness of staining agent. A transfer sheet was prepared by providing a film layer with a thickness of 3μ,
Next, using this transfer sheet, a transfer film of the staining agent was applied to the surface of a 3 mm thick plate glass with a cyclic substance (tin compound) dispersed in the surface layer by a heated roll transfer method, and the staining agent was transferred to the base film. After peeling off the (polyester film) from the transfer surface, the sheet glass was colored red with a uniform density over the entire surface by performing the same heating and firing process, cooling process, and firing residue removal process as in Example 12. I got it. Example 17 The staining agent ink obtained in Example 1 was further diluted by adding an appropriate amount of toluene, and measured using an Iwata viscometer.
An ink adjusted to a viscosity of 20 seconds was prepared, and then this ink was used to print an acrylic resin composition on a 16μ thick polyester film with a release layer formed on the surface using a gravure multicolor printing machine. On the surface of the release layer, a blurred pattern with a continuously varying print density is printed to form a printed film layer with a blurred pattern of the staining agent, and on top of this, a polyamide resin composition is also applied by gravure printing. A transfer sheet is prepared by providing a heat-sensitive adhesive layer consisting of the following: Next, using this transfer sheet, a transfer film of staining agent is applied to the surface of a 5 mm thick plate glass by a heated roll transfer method, and then a transfer film of a staining agent is applied to the surface of a 5 mm thick plate glass. After peeling off from the transfer surface, the same heating and firing process, cooling and cooling process, and firing residue removal process as in Example 11 were carried out, resulting in a shading-like pattern colored red with a continuous density gradient. A plate glass was obtained. Example 18 The staining agent ink obtained in Example 7 was further diluted by adding an appropriate amount of toluene and measured using an Iwata viscometer.
An ink adjusted to a viscosity of 20 seconds was prepared, and then this ink was applied onto a release layer (acrylic resin composition) of a 25μ polyester film provided with a release layer using a gravure multicolor printing machine. A transfer sheet was prepared by forming a printed film layer with a continuous tone pattern, and further providing a heat-sensitive adhesive layer made of a polyamide resin composition by gravure printing. Next, using this transfer sheet, the transfer layer (release layer, staining agent printed film layer, adhesive layer, etc.) of the transfer sheet is transferred by heating onto the alumina gel-coated surface of the alumina gel-coated glass bottle. After peeling off the polyester film from the transfer surface, it was heated in an electric furnace at 550°C for 20 minutes, slowly cooled, and then taken out of the furnace.Then, the glass bottle was immersed in a 1/20N aqueous solution of sulfuric acid. After washing with water, the firing residue of the staining agent remaining on the surface of the glass bottle was washed away to obtain a glass bottle having a continuous gradation pattern colored in red. Furthermore, even when the same transfer painting was performed on a glass bottle coated with silica gel instead of the alumina gel coat, a similar glass bottle colored red was obtained. Example 19 Using the viscosity-adjusted ink obtained in Example 17, a transfer sheet was prepared by spraying with a spray gun to provide a paint film layer with a shading pattern and a heat-sensitive adhesive layer, and the sheet was heated to 50°C in advance. After that, the surface of a 5 mm thick plate glass heated to 5 mm was subjected to a transfer process, a heating firing process, a cooling process, and a firing residue removal process in the same manner as in Example 17, thereby forming a shading pattern colored red. A plate glass was obtained. Example 20 Using the ink containing the staining agent obtained in Example 10, a printed film layer of the staining agent was printed over the entire surface by a gravure printing machine on the surface of a water-soluble base sheet made of polyvinyl alcohol with a thickness of 20μ. A water-soluble transfer sheet was prepared. Next, this transfer sheet is floated on the water surface (at room temperature) of a water tank prepared with the printed film layer of the staining agent facing upward, and the lower water-soluble base sheet is dissolved in the water and completely removed. When only the printed film layer of the staining agent remains, press the bottom of the glass bottle from above onto the printed film layer and allow it to settle under the water surface, thereby removing the printed film layer from the glass bottle using water pressure. After uniformly spreading the staining agent upward from the bottom of the outer surface of the glass bottle, when the glass bottle is pulled up from the water with the bottom facing upward, a printed film layer of the staining agent is evenly distributed on the outer surface of the glass bottle. Closely attached. Next, after drying this, the same heating and firing process, cooling process, firing residue removal process, etc. as in Example 11 were performed, and as a result, a glass bottle uniformly colored in red was obtained. In addition, instead of the uniform printed film layer made of staining agent ink provided on the above-mentioned water-soluble base sheet, a water-soluble transfer sheet is used in which a printed film layer with a blurred pattern with a density gradient is provided. Even if the glass bottle was treated in the same manner as above, a glass bottle having a red colored pattern with a shading pattern was obtained. Furthermore, when a plate glass having a thickness of 3 mm was used in place of the above-mentioned glass bottle and treated in the same manner, a plate glass having a shading pattern colored in red was obtained. Example 21 Using the ink containing the staining agent obtained in Example 9, a printed film layer of the staining agent was printed on the entire surface of a water-soluble base sheet made of methyl cellulose with a thickness of 30 μm using a gravure printing machine. Further, an adhesive layer made of a polyamide resin composition was provided thereon to prepare a water-soluble transfer sheet. Next, this transfer sheet is floated on the water surface (30℃) of a water tank prepared with the adhesive layer facing upwards, and when the lower water-soluble base sheet has dissolved more than 50%, a solvent is applied to the adhesive layer surface from above. After spraying an appropriate amount of (toluene/methyl alcohol, 1±1 mixed solvent) with a spray gun, while the adhesive layer dissolved by the solvent has not dried, the surface layer is coated with a tin compound from above. After pressing the plate glass in which the reducing substance has been injected and dispersed and allowing it to settle under the water surface, the printed film layer is uniformly spread along the surface of the plate glass together with the water-soluble film by water pressure, and then
The water-soluble film is completely dissolved and removed while pulling the plate glass out of the water with the spread side facing upward. Next, after drying this, the same heating and firing process, cooling process, firing residue removal process, etc. as in Example 12 were performed, and as a result, a plate glass whose entire surface was uniformly colored red was obtained. In addition, instead of the uniform printed film layer made of staining agent ink provided on the water-soluble base sheet, a water-soluble transfer sheet is used in which a printed film layer with a blurred pattern having a density gradient is provided. Even if the glass plate was treated in the same manner as above, a plate glass having a red colored pattern with a shading pattern was obtained.
Claims (1)
ー、溶剤及び必要により分散剤を添加混練してイ
ンク化してなることを特徴とするガラス着色用ス
テイニング剤。 ２ 銅の含ホウ素酸塩組成物粉末が、ホウ酸銅化
合物粉末である特許請求の範囲第１項記載のガラ
ス着色用ステイニング剤。 ３ ホウ酸銅化合物粉末が、各種ホウ酸銅、各種
ホウ酸銅のアルカリ錯塩、アンモニア錯塩、アミ
ン錯塩からなる群から選ばれた少なくとも１つの
銅化合物粉末である特許請求の範囲第２項記載の
ガラス着色用ステイニング剤。 ４ 銅の含ホウ素酸塩組成物粉末が、ホウフツ化
銅化合物粉末である特許請求の範囲第１項記載の
ガラス着色用ステイニング剤。 ５ ホウフツ化銅化合物粉末が、各種ホウフツ化
銅、各種ホウフツ化銅のアルカリ錯塩、アンモニ
ア錯塩、アミン錯塩からなる群から選ばれた少な
くとも１つの銅化合物粉末である特許請求の範囲
第４項記載のガラス着色用ステイニング剤。 ６ 銅の含ホウ素酸塩組成物粉末が、その中にフ
イラーを含有させたものである特許請求の範囲第
１項記載のガラス着色用ステイニング剤。 ７ 銅の含ホウ素酸塩組成物粉末が、ホウ酸銅化
合物粉末とホウフツ化銅化合物粉末との混合物で
ある特許請求の範囲第１項記載のガラス着色用ス
テイニング剤。 ８ 銅１重量部に対してホウ素が0.1及至１重量
部の割合の組成からなる銅の含ホウ素酸塩組成物
粉末に、必要によりフイラーを添加し、これに樹
脂バインダー、溶剤及び必要により分散剤を適量
添加し、これを混練して得たインク化してなるガ
ラス着色用ステイニング剤を、着色すべきガラス
の表面に全面又は任意の図柄に塗布又は印刷して
ステイニング剤の皮膜を形成した後、400℃〜800
℃に加熱焼成して発色させることを特徴とするガ
ラスの着色方法。 ９ 着色すべきガラスが、その表面部分に還元性
物質を有してなるものである特許請求の範囲第８
項記載のガラスの着色方法。 １０ 400℃〜800℃に加熱焼成することが、予め
設定された酸化性雰囲気〜還元性雰囲気中で行わ
れる特許請求の範囲第８項記載のガラスの着色方
法。 １１ ステイニング剤の皮膜が、部分的に銅の含
ホウ素酸塩組成物粉末量を増減させてなる着色剤
の濃淡部分を有してなる皮膜である特許請求の範
囲第８項記載のガラスの着色方法。 １２ 着色すべきガラスが、その表面部分に金属
酸化物層を有してなるものである特許請求の範囲
第８項記載のガラスの着色方法。 １３ 着色すべきガラスの表面にステイニング剤
を印刷する手段が、パツド印刷によるものである
特許請求の範囲第８項記載のガラスの着色方法。 １４ 銅１重量部に対してホウ素が0.1乃至１重
量部の割合の組成である銅の含ホウ素酸塩組成物
粉末に、必要によりフイラーを添加し、これに樹
脂バインダー、溶剤及び必要により分散剤を適量
添加し、これを混練して得たインク化してなるガ
ラス着色用ステイニング剤を、あらかじめ剥離処
理又は剥離層の施された基体シートの該剥離層面
上に全面又は任意の図柄に塗布又は印刷してステ
イニング剤の印刷皮膜層を形成し、その上に必要
により接着剤層を設けてなる転写シートを作り、
次いで該転写シートを着色すべきガラス表面に重
ね合わせて加熱、加圧してガラス表面に転写し、
400℃〜800℃に加熱焼成して発色させることを特
徴とするガラスの着色方法。 １５ 着色すべきガラスが、その表面に還元性物
質を有してなるものである特許請求の範囲第１４
項に記載のガラスの着色方法。 １６ 転写シートの印刷皮膜層が、部分的に銅の
含ホウ素酸塩組成物粉末量を増減させてなる着色
剤の濃淡部分を有してなる皮膜である特許請求の
範囲第１４項記載のガラスの着色方法。 １７ 銅１重量部に対してホウ素が0.1乃至１重
量部の割合の組成である銅の含ホウ素酸塩組成物
粉末に、必要によりフイラーを添加し、これに樹
脂バインダー、溶剤及び必要により分散剤を適量
添加し、これを混練して得たインク化してなるガ
ラス着色用ステイニング剤を、水溶性フイルム上
に全面又は任意の図柄に塗布又は印刷してステイ
ニング剤の印刷皮膜層を形成し、次いで水の存在
下において印刷皮膜層を着色すべきガラス表面に
付着させ、乾燥後400℃〜800℃に加熱焼成して発
色させることを特徴とするガラスの着色方法。 １８ 着色すべきガラスが、その表面に還元性物
質を有してなるものである特許請求の範囲第１７
項に記載のガラスの着色方法。 １９ 印刷皮膜層が、部分的に銅の含ホウ素酸塩
組成物粉末量を増減させてなる着色剤の濃淡部分
を有してなる皮膜である特許請求の範囲第１７項
記載のガラスの着色方法。[Scope of Claims] 1. A staining agent for glass coloring, which is prepared by adding and kneading a resin binder, a solvent, and, if necessary, a dispersant, to powder of a copper borate-containing salt composition to form an ink. 2. The staining agent for glass coloring according to claim 1, wherein the copper borate composition powder is a copper borate compound powder. 3. The copper borate compound powder according to claim 2, wherein the copper borate compound powder is at least one copper compound powder selected from the group consisting of various copper borates, various alkali complex salts of copper borate, ammonia complex salts, and amine complex salts. Staining agent for glass coloring. 4. The staining agent for glass coloring according to claim 1, wherein the copper borate composition powder is a copper borofluoride compound powder. 5. The copper borofluoride compound powder is at least one copper compound powder selected from the group consisting of various copper borofluorides, alkali complex salts of various copper borofluorides, ammonia complex salts, and amine complex salts. Staining agent for glass coloring. 6. The staining agent for glass coloring according to claim 1, wherein the copper borate composition powder contains a filler therein. 7. The staining agent for glass coloring according to claim 1, wherein the copper borate composition powder is a mixture of a copper borate compound powder and a copper borofluoride compound powder. 8 If necessary, filler is added to a copper boron-containing composition powder having a composition of 0.1 to 1 part by weight of boron per 1 part by weight of copper, and a resin binder, a solvent and, if necessary, a dispersant are added to this powder. A staining agent for glass coloring made by adding an appropriate amount of and kneading the resulting ink was applied or printed on the entire surface of the glass to be colored or in an arbitrary pattern to form a film of the staining agent. After, 400℃~800
A method for coloring glass, which is characterized by heating and firing at ℃ to develop color. 9. Claim 8, wherein the glass to be colored has a reducing substance on its surface.
Method for coloring glass as described in section. 10. The method for coloring glass according to claim 8, wherein the heating and firing at 400°C to 800°C is performed in a preset oxidizing atmosphere to reducing atmosphere. 11. The glass according to claim 8, wherein the coating of the staining agent is a coating formed by partially increasing or decreasing the amount of copper boron-containing salt composition powder and having dark and light areas of the coloring agent. Coloring method. 12. The method for coloring glass according to claim 8, wherein the glass to be colored has a metal oxide layer on its surface. 13. The method for coloring glass according to claim 8, wherein the means for printing the staining agent on the surface of the glass to be colored is by pad printing. 14 If necessary, a filler is added to a copper borate composition powder having a composition of 0.1 to 1 part by weight of boron per 1 part by weight of copper, and a resin binder, a solvent and, if necessary, a dispersant are added to this powder. A staining agent for glass coloring obtained by adding an appropriate amount of and kneading the resulting ink is applied to the entire surface or any desired pattern on the surface of the release layer of a base sheet that has been previously subjected to release treatment or a release layer. A transfer sheet is created by printing to form a printed film layer of staining agent, and then providing an adhesive layer thereon if necessary.
Next, the transfer sheet is placed on the glass surface to be colored, heated and pressed to transfer it to the glass surface,
A glass coloring method characterized by heating and firing at 400°C to 800°C to develop color. 15 Claim 14, wherein the glass to be colored has a reducing substance on its surface.
Method for coloring glass as described in section. 16. The glass according to claim 14, wherein the printed film layer of the transfer sheet is a film having light and dark areas of a colorant formed by partially increasing or decreasing the amount of copper borate composition powder. How to color. 17 If necessary, a filler is added to a copper borate composition powder having a composition of 0.1 to 1 part by weight of boron per 1 part by weight of copper, and a resin binder, a solvent and, if necessary, a dispersant are added to this powder. A staining agent for glass coloring obtained by adding an appropriate amount of and kneading the resulting ink is applied or printed on the entire surface or any desired pattern on a water-soluble film to form a printed film layer of the staining agent. A method for coloring glass, which is characterized in that a printed film layer is then attached to the surface of the glass to be colored in the presence of water, and after drying, the layer is heated and baked at 400°C to 800°C to develop color. 18 Claim 17, wherein the glass to be colored has a reducing substance on its surface.
Method for coloring glass as described in section. 19. The method for coloring glass according to claim 17, wherein the printed film layer is a film having light and dark areas of a coloring agent formed by partially increasing or decreasing the amount of copper borate composition powder. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5899480A JPS56155045A (en) | 1980-05-02 | 1980-05-02 | Stain for glass coloring and glass-coloring method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5899480A JPS56155045A (en) | 1980-05-02 | 1980-05-02 | Stain for glass coloring and glass-coloring method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56155045A JPS56155045A (en) | 1981-12-01 |
| JPS6353139B2 true JPS6353139B2 (en) | 1988-10-21 |
Family
ID=13100395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5899480A Granted JPS56155045A (en) | 1980-05-02 | 1980-05-02 | Stain for glass coloring and glass-coloring method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56155045A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58190841A (en) * | 1982-04-30 | 1983-11-07 | Okuno Seiyaku Kogyo Kk | Composition of coloring agent for glass |
| JPS62275041A (en) * | 1986-05-22 | 1987-11-30 | Hard Glass Kogyo Kk | Production of decorative reinforced glass |
| US6402823B1 (en) * | 2000-01-07 | 2002-06-11 | Ferro Corporation | Individual inks and an ink set for use in the color ink jet printing of glazed ceramic tiles and surfaces |
| GB2448338B (en) * | 2007-04-11 | 2012-02-29 | Dunwilco 1198 Ltd | Process for the preparation of coloured particulates |
-
1980
- 1980-05-02 JP JP5899480A patent/JPS56155045A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56155045A (en) | 1981-12-01 |
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