JPH02120042A - Heat-resistance indicating stock and label - Google Patents
Heat-resistance indicating stock and labelInfo
- Publication number
- JPH02120042A JPH02120042A JP63272789A JP27278988A JPH02120042A JP H02120042 A JPH02120042 A JP H02120042A JP 63272789 A JP63272789 A JP 63272789A JP 27278988 A JP27278988 A JP 27278988A JP H02120042 A JPH02120042 A JP H02120042A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- resistant
- layer
- pattern
- colorant
- 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.)
- Granted
Links
- 239000003086 colorant Substances 0.000 claims abstract description 18
- 238000005530 etching Methods 0.000 claims abstract description 17
- 229920006015 heat resistant resin Polymers 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 229920001721 polyimide Polymers 0.000 claims abstract description 11
- 239000004642 Polyimide Substances 0.000 claims abstract description 10
- 239000010410 layer Substances 0.000 claims description 64
- 239000012769 display material Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 20
- 239000012790 adhesive layer Substances 0.000 claims description 19
- 239000004593 Epoxy Substances 0.000 claims description 12
- 230000007261 regionalization Effects 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000011888 foil Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 8
- 238000004040 coloring Methods 0.000 abstract 1
- 239000003822 epoxy resin Substances 0.000 description 20
- 229920000647 polyepoxide Polymers 0.000 description 20
- -1 polyethylene terephthalate Polymers 0.000 description 12
- 230000001070 adhesive effect Effects 0.000 description 8
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 229920005575 poly(amic acid) Polymers 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000005907 alkyl ester group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000005011 phenolic resin Chemical class 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 3
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical class ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000011134 resol-type phenolic resin Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000001177 diphosphate Substances 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 210000004709 eyebrow Anatomy 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000012210 heat-resistant fiber Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000010680 novolac-type phenolic resin Substances 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920003055 poly(ester-imide) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 239000012056 semi-solid material Substances 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 125000005624 silicic acid group Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、レーザー光線により高密度なエツチングパタ
ーンを形成できるようにした耐熱性表示素材、及びそれ
を用いた耐擦過性、耐熱性、耐久性、柔軟性、耐薬品性
に優れるラベルに関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a heat-resistant display material capable of forming a high-density etching pattern with a laser beam, and a display material using the same that exhibits scratch resistance, heat resistance, durability, and flexibility. Regarding labels with excellent durability and chemical resistance.
発明の背景
多品種少量生産へと生産体制が変遷するなか、耐熱性プ
ラスチックや金属さらにガラスや焼成セラミックなどか
らなる製品、あるいは半製品や部品等の管理に用いる識
別ラベルとして、これまでの焼成セラミックやステンレ
ス、はうろう体などからなる基板タイプのものを用いる
のでは、ビス止め等による固着手間の問題、剛性による
曲面固着性欠如の問題、現場等でのパターン付与による
識別ラベルの臨機形成性欠如の問題などがあるため、新
たなタイプの識別ラベルが要望されている。Background of the Invention As production systems shift to high-mix, low-volume production, fired ceramics have become increasingly popular as identification labels used to manage products made of heat-resistant plastics, metals, glass, and fired ceramics, as well as semi-finished products and parts. When using a substrate type made of aluminum, stainless steel, or a floating body, there are problems with fixing time due to screws, etc., lack of fixation on curved surfaces due to rigidity, and flexibility in forming identification labels by applying patterns on-site. Due to problems such as lack of identification, new types of identification labels are required.
新タイプの識別ラベルに要求される基本的な性能は、パ
ターンの高密度性、耐擦過性、簡便接着性、柔軟性、臨
機なラベル形成性、耐熱性、耐薬品性などである。The basic performance requirements for new types of identification labels include high pattern density, scratch resistance, easy adhesion, flexibility, flexible label formation, heat resistance, and chemical resistance.
従来の技術及び課題
従来、前記に応える識別ラベルとして、ポリエチレンテ
レフタレートの如きプラスチックフィルム、ないしその
金属蒸着物や紙等からなる印刷用基材に、熱転写プリン
タでパターンを付与したものが提案されている。Conventional Technologies and Problems Conventionally, as an identification label that meets the above-mentioned requirements, it has been proposed to use a thermal transfer printer to apply a pattern to a printing base material made of a plastic film such as polyethylene terephthalate, or a metal-deposited product thereof, or paper. .
しかしながら、その印刷用基材の耐熱性が熱転写プリン
タによる加熱温度に耐える程度のものであり、相対的に
耐熱性に乏しい問題点があった。However, the heat resistance of the printing base material is such that it can withstand the heating temperature of a thermal transfer printer, and there is a problem in that the heat resistance is relatively poor.
また、形成したパターンが耐擦過性に乏しい問題点もあ
った。さらに、プリンタの印字等の性能の限界から高密
度なパターン形成性に乏しい問題点もあった。There was also the problem that the formed pattern had poor scratch resistance. Furthermore, there was also the problem that high-density pattern formation was poor due to the limitations of printer performance such as printing.
課題を解決するための手段
本発明は、レーザー光線によるエツチングパターンの形
成を可能として上記の課題を克服したものである。Means for Solving the Problems The present invention overcomes the above problems by making it possible to form etching patterns using laser beams.
すなわち、本発明は、耐熱性ベース層の上に、エツチン
グパターンの形成処理を受ける着色剤含有の耐熱性樹脂
層からなる被マーキング層を有する複層柔軟基材の裏面
に、被着体への仮着が可能な耐熱性接着層を有すること
を特徴とする耐熱性表示素材、及び
前記の耐熱性表示素材における被マーキング層に、レー
ザー光線によるエツチングパターンを形成してなること
を特徴とするラベルを提供するものである。That is, the present invention provides a method for forming an adhesive onto an adherend on the back side of a multilayer flexible base material having a marking layer made of a colorant-containing heat-resistant resin layer that is subjected to an etching pattern formation process on a heat-resistant base layer. A heat-resistant display material characterized by having a heat-resistant adhesive layer that can be temporarily attached, and a label characterized by forming an etching pattern using a laser beam on the marking layer of the heat-resistant display material. This is what we provide.
作用
耐熱性ベース層の上に着色剤含有の耐熱性樹脂層からな
る被マーキング層を設けることにより、レーザー光線を
用いて高密度かつ高精度で、耐擦過性に優れるエツチン
グパターンを臨機に形成することができる。しかも、得
られたラベルはががる素材の柔軟性とその耐熱性接着層
に基づいて、被着体への簡便接着性、曲面接着性を示し
、また耐熱性、耐薬品性、耐久性に優れている。By providing a marking layer made of a heat-resistant resin layer containing a colorant on the heat-resistant base layer, an etching pattern with high density, high precision, and excellent scratch resistance can be formed using a laser beam. Can be done. Moreover, based on the flexibility of the removable material and its heat-resistant adhesive layer, the resulting label exhibits easy adhesion to adherends and curved surface adhesion, as well as excellent heat resistance, chemical resistance, and durability. Are better.
発明の構成要素の例示
本発明の耐熱性表示素材は、耐熱性ベース層の片面に被
マーキング層を有し、他面に耐熱性接着層を有してなる
。その構造例を第１図に示した。Examples of Constituent Elements of the Invention The heat-resistant display material of the present invention has a heat-resistant base layer, a marking layer on one side, and a heat-resistant adhesive layer on the other side. An example of its structure is shown in FIG.
１が被マーキング層、２が耐熱性ベース層、３が耐熱性
接着層であり、被マーキング層１と耐熱性ベース層２が
複層柔軟基材を形成する。1 is a layer to be marked, 2 is a heat-resistant base layer, and 3 is a heat-resistant adhesive layer, and the layer to be marked 1 and the heat-resistant base layer 2 form a multilayer flexible base material.
被マーキング層は、レーザー光線などを用いてエツチン
グパターンが形成される層であり、着色剤含有の耐熱性
樹脂層で形成される。層厚は適宜に決定してよいが、通
常５００ ｍｍ以下、就中ｌＯ〜２００趨で充分である
。The marking layer is a layer on which an etching pattern is formed using a laser beam or the like, and is formed of a heat-resistant resin layer containing a colorant. Although the layer thickness may be determined as appropriate, it is usually sufficient to have a thickness of 500 mm or less, particularly in the range of lO to 200 mm.
耐熱性樹脂としては、柔軟で耐熱性、熱寸法安定性に優
れる膜形成能を有するものが用いられる。As the heat-resistant resin, one that is flexible and has film-forming ability with excellent heat resistance and thermal dimensional stability is used.
就中、１５０℃以上の耐熱性を有し、熱収縮率が１．５
％以下のものが好ましく用いられる。その例としてはポ
リイミド、ポリエーテルエーテルケトン、ポリエーテル
サルフォン、ポリエーテルイミド、ポリサルフォン、ポ
リフェニレンサルファイド、ポリアミドイミド、ポリエ
ステルイミド、芳香族ポリアミド、ポリパラバン酸、フ
ッ素樹脂、エポキシ樹脂などがあげられる。就中、ポリ
イミドが好ましく用いられる。In particular, it has heat resistance of 150℃ or higher and a heat shrinkage rate of 1.5.
% or less is preferably used. Examples include polyimide, polyetheretherketone, polyethersulfone, polyetherimide, polysulfone, polyphenylene sulfide, polyamideimide, polyesterimide, aromatic polyamide, polyparabanic acid, fluororesin, and epoxy resin. Among these, polyimide is preferably used.
被マーキング層に配合する着色剤は、層の不透明化、な
いし有色化による形成パターン認識性の向上を目的とす
る。従って、有色物質であればよい。好ましく用いつる
着色剤の例としては、炭化ケイ素、窒化ケイ素、窒化ホ
ウ素、アルミナ、ジルコニア、酸化ケイ素、チタニア、
チタン酸バリウムの如きセラミック粉末、鉄粉、クロム
粉、銀粉、金粉の如き金属粉末、ＭｎＯ２Ｃｒ２Ｏ３、
Ｃｏｏ−Ｍｎ０２−ＣｒＯ−Ｆｅ２０３、Ｎｉ０ｚ −
ＣｒＯ３、Ｃｏｏ Ａｌ１０３ 、カーボンブラック
の如き顔料などがあげられる。その他、種々の顔料ない
し染料なども用いうる（染料便覧、顔料表記載物、１９
７０年丸善−発行）。粉末の粒径は１００μｍ以下、就
中５ｈｍ以下が適当である。着色剤の配合量は、耐熱性
樹脂１００重量部あたり０．１〜１００重量部が一般で
ある。The purpose of the coloring agent added to the marking layer is to make the layer opaque or colored, thereby improving the recognizability of the formed pattern. Therefore, any colored substance may be used. Examples of preferably used vine colorants include silicon carbide, silicon nitride, boron nitride, alumina, zirconia, silicon oxide, titania,
Ceramic powder such as barium titanate, metal powder such as iron powder, chromium powder, silver powder, gold powder, MnO2Cr2O3,
Coo-Mn02-CrO-Fe203, Ni0z −
Examples include pigments such as CrO3, CooAl103, and carbon black. In addition, various pigments or dyes can also be used (see Dye Handbook, Pigment List, 19
Published by Maruzen in 1970). The particle size of the powder is preferably 100 μm or less, particularly 5 hm or less. The amount of the colorant to be blended is generally 0.1 to 100 parts by weight per 100 parts by weight of the heat-resistant resin.
被マーキング層の形成は、例えば溶液や溶融液等とした
液状の耐熱性樹脂と着色剤との混合物を耐熱性ベース層
の上に展開し、造膜処理する方式など、適宜な方式で行
ってよい。なお、ポリイミドからなる被マーキング層を
形成する場合には、ポリイミドの前駆体であるポリアミ
ド酸の有機溶媒溶液に着・色剤を配合し、その混合液を
展開して加熱処理し、脱水閉環反応によりイミド化させ
て硬化する方式が適当である。The layer to be marked is formed by an appropriate method, such as by spreading a mixture of a liquid heat-resistant resin and a colorant in the form of a solution or melt onto the heat-resistant base layer and forming a film. good. In addition, when forming a marking layer made of polyimide, a coloring agent is added to an organic solvent solution of polyamic acid, which is a precursor of polyimide, and the mixture is developed and heat-treated to undergo a dehydration ring-closing reaction. A method of curing by imidization is suitable.
そのポリアミド酸の有機溶媒溶液としては、通常の芳香
族テトラカルボン酸二無水物とジアミノ化合物からなる
ものと、Ｎ−メチル−２−ピロリドンの如き有機極性溶
媒との溶液を用いつる。ポリイミド自体の無色透明性に
基づく配合着色剤の色発現性の点よりは、ビフェニルテ
トラカルボン酸二無水物と、メタ位にアミノ基を有する
芳香族ジアミンよりなるポリアミド酸が好ましく用いら
れる。溶媒としてはジメチルアセトアミドの如きアミド
系有機極性溶媒が好ましく用いられる。As the organic solvent solution of the polyamic acid, a solution of a usual aromatic tetracarboxylic dianhydride and a diamino compound and an organic polar solvent such as N-methyl-2-pyrrolidone can be used. From the point of view of color development of the blended colorant based on the colorless transparency of the polyimide itself, a polyamic acid composed of biphenyltetracarboxylic dianhydride and an aromatic diamine having an amino group at the meta position is preferably used. As the solvent, an amide organic polar solvent such as dimethylacetamide is preferably used.
前記の好ましく用いうるポリアミド酸の例としては、下
記の一般式で表されるものがあげられる（特開昭６２−
７７３３号公報）。Examples of the above-mentioned preferably usable polyamic acids include those represented by the following general formula (Japanese Patent Application Laid-Open No. 1983-1999)
Publication No. 7733).
一般式：
（ただし、
Ｘは、−ゆｒＹｌ−◎−；
Ｃ（ＣＦ ３）２ 又１ｔＣＯ； Ｙ２はｃ（ＣＨａ）
ａ、ＳＯ２又はＣ（ＣＦ３ ）２ ； Ｙ３、Ｙ’ 、
Ｙ５、Ｙ’はＨ，Ｆ、ＣＩ、ＣＨ３、Ｃ２Ｈ５、ＮＯ２
又はＣＦ ３である。）
被マーキング層を形成するに際しては、耐熱性ベース層
との接着力の向上など、種々の目的から必要に応じて適
宜な添加剤を配合してもよい。例えば、エポキシ系化合
物の添加は、耐擦過性、耐熱性、接着力の向上などに有
効である。用いるエポキシ系化合物は分子中に２個以上
のエポキシ基を有するものが好ましい。その添加量は適
宜に決定してよい。ポリイミドからなる被マーキング層
を形成する場合には、その前駆体であるポリアミド酸の
カルボキシル基１当量に対しエポキシ基が０．３当量以
上の割合となるよう添加することが好ましい。General formula: (However, X is -YrYl-◎-; C(CF3)2 or 1tCO; Y2 is c(CHa)
a, SO2 or C(CF3)2; Y3, Y',
Y5, Y' are H, F, CI, CH3, C2H5, NO2
Or CF3. ) When forming the marking layer, appropriate additives may be added as necessary for various purposes such as improving adhesive strength with the heat-resistant base layer. For example, addition of an epoxy compound is effective in improving scratch resistance, heat resistance, adhesive strength, and the like. The epoxy compound used preferably has two or more epoxy groups in the molecule. The amount added may be determined as appropriate. When forming a marking layer made of polyimide, it is preferable to add epoxy groups at a ratio of 0.3 or more equivalents to 1 equivalent of carboxyl groups of the polyamic acid precursor.
耐熱性ベース層は、被マーキング層をエツチング処理し
てなるパターンの支持機能を担い、耐熱性のフレキシブ
ル材料で形成される。一般には、上記した耐熱性樹脂か
らなるフィルムや、アルミニウム等の金属からなる箔な
どで形成される。耐熱性ベース層は、必要に応じ２層以
上の積層構造として物理的、ないし化学的性質が調節さ
れる。The heat-resistant base layer has the function of supporting a pattern formed by etching the layer to be marked, and is formed of a heat-resistant flexible material. Generally, it is formed of a film made of the above-mentioned heat-resistant resin, a foil made of metal such as aluminum, or the like. The heat-resistant base layer has a laminated structure of two or more layers and its physical or chemical properties are adjusted as necessary.
耐熱性ベース層を耐熱性樹脂で形成する場合には、被マ
ーキング層の場合と同様、例えばエポキシ系化合物など
の適宜な添加剤を必要に応じ配合してよい。被マーキン
グ層をエツチング処理してなるパターンの認識性の向上
をはかる点よりは、耐熱性ベース層の少なくとも被マー
キング層側表面に、色調変化等のコントラストをもたせ
ることが好ましい。被マーキング層の形成に用いた着色
剤とは異なる色の着色剤を耐熱性ベース層に混入させる
方式、色違い着色剤の含有層を表面に有する耐熱性ベー
ス層とする方式など、適宜な方式でコントラストを付与
してよい。耐熱性ベース層の層厚は、使用目的や、柔軟
性などに応じ適宜に決定してよい。一般には１１Ｉｗ以
下、就中５００μｍ以下とされる。When the heat-resistant base layer is formed of a heat-resistant resin, suitable additives such as epoxy compounds may be added as necessary, as in the case of the marked layer. In order to improve the recognizability of the pattern obtained by etching the marking layer, it is preferable that at least the surface of the heat-resistant base layer on the marking layer side has a contrast such as a change in color tone. An appropriate method may be used, such as a method in which a coloring agent of a different color from the colorant used to form the marking layer is mixed into the heat-resistant base layer, or a method in which the heat-resistant base layer has a layer containing a colorant of a different color on its surface. You can add contrast. The thickness of the heat-resistant base layer may be determined as appropriate depending on the purpose of use, flexibility, etc. It is generally 11 Iw or less, particularly 500 μm or less.
なお、被マーキング層と耐熱性ベース層からなる複層柔
軟基材は、形成されるパターンの認識性の点より、当該
眉間における反射率の相違に基づき、波長４００〜９０
０ｎｍの光に対するＰＣ８値（最小反射率）が２５％以
上、就中５０％以上となるよう形成することが好ましい
。ＰＣ８値は、各層の厚さや、着色剤の種類ないし配合
量等を制御することにより調節することができる。In addition, from the viewpoint of recognition of the formed pattern, the multilayer flexible base material consisting of the marking layer and the heat-resistant base layer has a wavelength of 400 to 90, based on the difference in reflectance between the eyebrows.
It is preferable to form the film so that the PC8 value (minimum reflectance) for light of 0 nm is 25% or more, particularly 50% or more. The PC8 value can be adjusted by controlling the thickness of each layer, the type and amount of colorant, etc.
耐熱性接着層は、複層柔軟基材の裏面、すなわち耐熱性
ベース層の露出側に、被着体に仮着できるよう設けられ
る。接着剤には耐熱性の点よりエポキシ樹脂、ないしそ
の含有物、又はシリコーン系感圧接着剤が好ましく用い
られる。エポキシ樹脂としては、グリシジルエーテル型
、グリシジルエステル型、グリシジルアミン型、線状脂
肪族エポキシド型、脂環族エポキシド型などの公知物を
用いてよい。硬化剤としては、加熱により硬化作用を発
揮するものが用いられ、就中５０〜２００℃で硬化作用
を発揮するものが用いられる。その例としては、ジシア
ンジアミド、４，４′−ジアミノジフェニルスルホン、
２−ｎ−ヘプタデシルイミダゾール等のイミダゾール誘
導体、イソフタル酸ジヒドラジド、Ｎ、Ｎ−ジアルキル
尿素誘導体、Ｎ。The heat-resistant adhesive layer is provided on the back side of the multilayer flexible base material, that is, on the exposed side of the heat-resistant base layer, so that it can be temporarily attached to an adherend. From the viewpoint of heat resistance, an epoxy resin or a material containing it, or a silicone pressure-sensitive adhesive is preferably used as the adhesive. As the epoxy resin, known resins such as glycidyl ether type, glycidyl ester type, glycidyl amine type, linear aliphatic epoxide type, and alicyclic epoxide type may be used. As the curing agent, one that exhibits a curing effect upon heating is used, and in particular, one that exhibits a curing effect at 50 to 200°C is used. Examples include dicyandiamide, 4,4'-diaminodiphenylsulfone,
Imidazole derivatives such as 2-n-heptadecyl imidazole, isophthalic acid dihydrazide, N,N-dialkyl urea derivatives, N.
Ｎ−ジアルキルチオ尿素誘導体、酸無水物系化合物、フ
ェノール樹脂系化合物、芳香族アミン系化合物などがあ
げられる。硬化剤の使用量は、エポキシ樹脂１００重量
部あたり１〜１５重量部が適当である。Examples include N-dialkylthiourea derivatives, acid anhydride compounds, phenol resin compounds, and aromatic amine compounds. The appropriate amount of the curing agent used is 1 to 15 parts by weight per 100 parts by weight of the epoxy resin.
プレス時に潤滑油が付着したり、防錆油で処理されたり
することのある金属製品などのように、油面接着性が要
求される場合には、長鎖アルキル主鎖を有する液状ない
し半固形状のエポキシ樹脂、又は液状ないし半固形状の
エポキシ樹脂にビスフノールＡとエピクロルヒドリンの
誘導体からなる高分子量の熱可塑性樹脂を配合したもの
が好ましく用いられる。これらのエポキシ樹脂は、鎖状
構成分子が油脂弁との良好な相溶性を示して油面に対し
優れた初期接着性を示す。また、凝集力を高めて粘着シ
ート形成性も向上させる。油面接着性の向上には、ゴム
系樹脂の併用も有効である。特に、イソブチレンゴム、
イソプレンゴム、ブタジェンゴム、クロロプレンゴム、
ニトリル・ブタジェンゴムの如きＳＰ値が７〜９．６の
ゴム系樹脂が好ましく用いられる。ゴム系樹脂の使用量
はエポキシ樹脂の５〜４０重量％が適当である。When oil surface adhesion is required, such as metal products that may be coated with lubricating oil during pressing or treated with anti-rust oil, liquid or semi-solid materials with long alkyl main chains are used. Preferably used are epoxy resins in the form of epoxy resins or liquid or semi-solid epoxy resins blended with high molecular weight thermoplastic resins made of bisphenol A and epichlorohydrin derivatives. These epoxy resins have chain molecules that exhibit good compatibility with oil valves and exhibit excellent initial adhesion to oil surfaces. It also increases the cohesive force and improves adhesive sheet formability. The combined use of rubber resin is also effective in improving the adhesion to oil surfaces. In particular, isobutylene rubber,
Isoprene rubber, butadiene rubber, chloroprene rubber,
A rubber resin having an SP value of 7 to 9.6, such as nitrile-butadiene rubber, is preferably used. The appropriate amount of rubber resin to be used is 5 to 40% by weight of the epoxy resin.
一方、種々の被着体に対する初期接着性に優れる粘着性
のエポキシ系の耐熱性接着層が要求される場合には、ア
クリル系樹脂の併用が好ましい。On the other hand, when a heat-resistant epoxy adhesive layer with excellent initial adhesion to various adherends is required, it is preferable to use an acrylic resin in combination.
その使用量はエポキシ樹脂１００重量部あたり２５〜２
５０重量部が適当である。アクリル系樹脂としては、ア
クリル酸ないしメタクリル酸のアルキルエステルと官能
基含有モノマからなる重量平均分子量約１０万〜約２０
０万の、加熱時における感圧接着性の良好な共重合体が
好ましく用いられる。その共重合体の調製に用いられる
アクリル酸ないしメタクリル酸のアルキルエステル、す
なわちアクリル酸系のアルキルエステルの例としては、
メチル基、エチル基、ブチル基、２−エチルへキシル基
、オクタデシル基の如き炭素数１〜ＩＯのアルキル基を
有するものがあげられる。官能基含有モノマの例として
は、アクリル酸、メタクリル酸、クロトン酸、マレイン
酸、イタコン酸の如きカルボキシル基含有モノマ、２−
ヒドロキシエチル基、２−ヒドロキシプロピル基を有す
るアクリル酸系のエステルの如きヒドロキシル基含有モ
ノマ、アクリルアミド、メタクリルアミドの如きアミノ
基含有モノマなどがあげられる。共重合体の調製に際し
ては必要に応じ、スチレン、酢酸ビニル、アクリロニト
リル、メタクリロニトリルの如き通例の改質モノマを用
いてよい。アクリル系樹脂は、これに官能基含有モノマ
を介し導入した官能基に基づき架橋しうる組成で併用さ
れる。架橋処理には、エポキシ系の耐熱性接着層の形成
に用いたエポキシ樹脂を利用してもよいし、架橋成分を
別途に添加してもよい。別途添加の架橋成分としては、
エポキシ樹脂、レゾール系フェノール樹脂の如き直接反
応型のものや、ポリイソシアネート、ポリアミン、メラ
ミン等の架橋剤を介し架橋反応に関与するキシレン樹脂
、ロジン、ノボラック系ないしレゾール系のフェノール
樹脂、ロジン変性フェノール樹脂、テルペン変性フェノ
ール樹脂、無水マレイン酸変性石油樹脂の如き官能性樹
脂などが用いられる。アクリル系樹脂との相溶性が良好
で、融点が８０〜１５０℃の架橋成分が好ましく用いら
れる。The amount used is 25 to 2 parts per 100 parts by weight of epoxy resin.
50 parts by weight is suitable. The acrylic resin has a weight average molecular weight of about 100,000 to about 20, consisting of an alkyl ester of acrylic acid or methacrylic acid and a functional group-containing monomer.
A copolymer having good pressure-sensitive adhesive properties when heated is preferably used. Examples of alkyl esters of acrylic acid or methacrylic acid, that is, acrylic acid-based alkyl esters, used in the preparation of the copolymer include:
Examples include those having an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a butyl group, a 2-ethylhexyl group, and an octadecyl group. Examples of functional group-containing monomers include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, 2-
Examples include hydroxyl group-containing monomers such as acrylic acid esters having a hydroxyethyl group and 2-hydroxypropyl group, and amino group-containing monomers such as acrylamide and methacrylamide. In preparing the copolymer, customary modifying monomers such as styrene, vinyl acetate, acrylonitrile, and methacrylonitrile may be used, if necessary. The acrylic resin is used in combination with a composition that can be crosslinked based on the functional group introduced therein via a functional group-containing monomer. For the crosslinking treatment, the epoxy resin used to form the epoxy heat-resistant adhesive layer may be used, or a crosslinking component may be added separately. As a separately added crosslinking component,
Direct reaction types such as epoxy resins and resol type phenolic resins, xylene resins that participate in crosslinking reactions via crosslinking agents such as polyisocyanates, polyamines, and melamine, rosin, novolac type or resol type phenolic resins, and rosin-modified phenols. Functional resins such as resins, terpene-modified phenolic resins, and maleic anhydride-modified petroleum resins are used. A crosslinking component that has good compatibility with the acrylic resin and has a melting point of 80 to 150°C is preferably used.
エポキシ系の耐熱性接着層は、要求される性能に応じ前
記した各成分が適宜に組合されて形成される。その形成
に際しては必要に応じ、粘着シート成形が可能な程度に
凝集力を持たせたり、流動（タレ）防止性を付与したり
、溶融粘度を下げてぬれ性を向上させたりすることなど
を目的として適宜な添加剤が配合される。粘着シート成
形の点よりは、例えばポリビニルブチラール、ポリアミ
ドないしその誘導体、ポリエステル、ポリスルホン、ポ
リケトン、ビスフェノールＡとエピクロルヒドリンの誘
導体からなる高分子量エポキシ樹脂等の熱可塑性樹脂、
ブタジェン・アクリロニトリル共重合体ないしその誘導
体などが用いられる。The epoxy heat-resistant adhesive layer is formed by appropriately combining the above-mentioned components depending on the required performance. When forming it, the purpose is to provide cohesive strength to the extent that it can be formed into an adhesive sheet, to provide flow (sag) prevention properties, and to improve wettability by lowering melt viscosity, as necessary. Appropriate additives are added. From the viewpoint of adhesive sheet molding, thermoplastic resins such as polyvinyl butyral, polyamide or its derivatives, polyester, polysulfone, polyketone, high molecular weight epoxy resins made of bisphenol A and epichlorohydrin derivatives,
Butadiene-acrylonitrile copolymer or its derivatives are used.
その使用量は、エポキシ樹脂１００重量部あたり５〜１
００重量部が適当である。タレ防止の点よりは、炭酸カ
ルシウム、タルク、耐熱性繊維、ケイ酸類、カーボンブ
ラック、コロイダルシリカなどの充填剤が用いられる。The amount used is 5 to 1 per 100 parts by weight of epoxy resin.
00 parts by weight is suitable. From the viewpoint of preventing sagging, fillers such as calcium carbonate, talc, heat-resistant fibers, silicic acids, carbon black, and colloidal silica are used.
その使用量はエポキシ樹脂１００重量部あたり１０〜３
００重量部が適当である。ぬれ性向上の点よりは、ブチ
ルグリシジルエーテル、長鎖アルコールのモノグリシジ
ルエーテルの如き反応性希釈剤、ジオクチルフタレート
の如きフタル酸系可塑剤、トリクレンジホスフェートの
如きリン酸系可ｖ剤などが用いられる。その使用量はエ
ポキシ樹脂１００重量部あたり５〜３０重量部が適当で
ある。The amount used is 10 to 3 parts per 100 parts by weight of epoxy resin.
00 parts by weight is suitable. From the point of view of improving wettability, reactive diluents such as butyl glycidyl ether and long-chain alcohol monoglycidyl ether, phthalic acid plasticizers such as dioctyl phthalate, phosphoric acid plasticizers such as triclean diphosphate, etc. are used. It will be done. The appropriate amount to be used is 5 to 30 parts by weight per 100 parts by weight of the epoxy resin.
シリコーン系感圧接着剤としては特に限定はな（、いず
れの公知物も用いつる。The silicone pressure-sensitive adhesive is not particularly limited (any known material may be used).
複層柔軟基材に設ける耐熱性接着層の厚さは５〜３００
μｍが一般的であるが、これに限定されず適宜に決定し
てよい。耐熱性接着層の形成は、その形成剤を塗工する
方式や、形成剤からなるシートを予め形成し、これを複
層柔軟基材に接着する方式などがあげられる。エポキシ
系の耐熱性接着層の場合、その粘度が低くて流動するよ
うな場合には、エポキシ樹脂等を半硬化させるなどして
粘度を高めてもよい。耐熱性接着層の露出面は必要に応
じセパレータ等で被覆保護して、パターン形成などに供
される。The thickness of the heat-resistant adhesive layer provided on the multilayer flexible base material is 5 to 300 mm.
Although it is generally μm, it is not limited to this and may be determined as appropriate. The heat-resistant adhesive layer can be formed by applying a forming agent, or by forming a sheet made of a forming agent in advance and bonding it to a multilayer flexible base material. In the case of an epoxy-based heat-resistant adhesive layer, if its viscosity is low and it flows, the viscosity may be increased by semi-curing the epoxy resin or the like. The exposed surface of the heat-resistant adhesive layer is covered and protected with a separator or the like as necessary, and then used for pattern formation.
なお、耐熱性接着層に必要に応じ、着色剤を配合して光
の反射率を向上させてもよい。シリコーン系感圧接着剤
の場合、初期タックの保持性の点より着色剤の配合量は
５０重量％以下が適当である。Note that, if necessary, a colorant may be added to the heat-resistant adhesive layer to improve the light reflectance. In the case of silicone-based pressure-sensitive adhesives, from the viewpoint of initial tack retention, the amount of colorant added is preferably 50% by weight or less.
本発明の耐熱性表示素材は、被着体に仮着できる耐熱性
の表示用紙として用いることができる。The heat-resistant display material of the present invention can be used as a heat-resistant display paper that can be temporarily attached to an adherend.
特に、第２図に例示したように、適宜なサイズに成形し
て識別ラベル等、耐熱性のラベルの形成に好ましく用い
られる。In particular, as illustrated in FIG. 2, it is preferably used for forming heat-resistant labels such as identification labels by molding them into appropriate sizes.
ラベルの形成は例えば、耐熱性表示素材における被マー
キング層にバーコード等の所定のパターンをレーザー光
線などを用いてエツチング形成することにより行うこと
ができる。第２図は、耐熱性表示素材における被マーキ
ング層１をレーザー光線でエツチング処理し、パターン
層４を形成してなるラベルを例示したものである。パタ
ーンは適宜なエツチング方式で形成することができる。The label can be formed, for example, by etching a predetermined pattern such as a bar code on the marking layer of the heat-resistant display material using a laser beam or the like. FIG. 2 shows an example of a label in which a patterned layer 4 is formed by etching the marking layer 1 of a heat-resistant display material with a laser beam. The pattern can be formed by any suitable etching method.
形成するパターンは任意である。レーザー光線によるエ
ツチングパターン形成方式が、パターンの形成密度や精
度などの点で好ましい。Ｎｄ： Ｙ Ａ Ｇレーザ、Ｎ
ｄニガラスレーザ、Ｃｒ：Ａｌ２Ｏ：＋レーザ、ＣＯ２
レーザなど、適宜な加工用レーザー装置を用いてパター
ンを形成することができる。Any pattern can be formed. An etching pattern formation method using a laser beam is preferable in terms of pattern formation density and accuracy. Nd: Y A G laser, N
dNiglas laser, Cr:Al2O:+ laser, CO2
The pattern can be formed using an appropriate processing laser device such as a laser.
ラベルの被着体への接着処理は、耐熱性表示素材におけ
る耐熱性接着層を介して行われる。シリコーン系感圧接
着層の場合には圧着するだけでよいし、エポキシ系の耐
熱性接着層の場合には、仮着後５０〜４００℃で加熱処
理される。加熱処理により、エポキシ系の耐熱性接着層
が硬化して被着体に強固に接着し、耐薬品性も向上する
。The label is bonded to the adherend through a heat-resistant adhesive layer in the heat-resistant display material. In the case of a silicone-based pressure-sensitive adhesive layer, it is sufficient to simply press-bond it, and in the case of an epoxy-based heat-resistant adhesive layer, it is heat-treated at 50 to 400°C after temporary adhesion. By heat treatment, the epoxy-based heat-resistant adhesive layer is cured and firmly adheres to the adherend, and chemical resistance is also improved.
なおラベルは、耐熱性表示素材をその耐熱性接着層を介
し被着体に仮着、ないし接着したのち、その被マーキン
グ層にエツチングパターンを形成する方法によっても行
うことができる。Note that the label can also be formed by a method in which a heat-resistant display material is temporarily attached or adhered to an adherend via its heat-resistant adhesive layer, and then an etching pattern is formed on the marking layer.
発明の効果
本発明の耐熱性表示素材は、簡便接着性、柔軟性、耐熱
性、耐薬品性に優れる。また、レーザー光線等によるエ
ツチング処理でパターンが形成されるようにしたので、
高密度で高精度のパターンを臨機に形成することができ
、形成されたパターンは耐擦過性に優れている。Effects of the Invention The heat-resistant display material of the present invention is excellent in simple adhesiveness, flexibility, heat resistance, and chemical resistance. In addition, the pattern was formed by etching using a laser beam, etc.
High-density, high-precision patterns can be formed at any time, and the formed patterns have excellent scratch resistance.
（以下余白）
実施例
参考例１〜４３
１ｅのセパラブルフラスコに表に示す溶媒とジアミノ化
合物を入れ、室温で十分に混合して溶液とした。溶媒の
使用量は、ジアミノ化合物と芳香族テトラカルボン酸二
無水物のモノマー濃度が２０重量％となるよう設定した
。(Margin below) Examples Reference Examples 1 to 43 The solvent and diamino compound shown in the table were placed in a separable flask of 1e, and thoroughly mixed at room temperature to form a solution. The amount of solvent used was set so that the monomer concentration of the diamino compound and aromatic tetracarboxylic dianhydride was 20% by weight.
次に、前記の溶液に同表に示す芳香族テトラカルボン酸
二無水物を、発熱による温度上昇を抑制しつつ徐々に添
加したのち、室温で４時間撹拌下に反応させ、同表に示
す対数粘度のポリアミド酸の溶液を得た。Next, the aromatic tetracarboxylic dianhydride shown in the same table was gradually added to the above solution while suppressing the temperature rise due to heat generation, and the reaction was carried out with stirring at room temperature for 4 hours. A solution of viscous polyamic acid was obtained.
Ｙｌ：イエローインデックス（ＳＭカラーコンピュータ
にて測定；スガ試験器社製）；この値が大きいほど黄色
度が高い。Yl: Yellow index (measured with an SM color computer; manufactured by Suga Test Instruments Co., Ltd.); the larger this value, the higher the degree of yellowness.
透過度（分光光度計で波長５００ｎｍにつき測定；島津
製作所社製）：この値が大きいほど透明度が高い。Transmittance (measured with a spectrophotometer at a wavelength of 500 nm; manufactured by Shimadzu Corporation): The larger this value is, the higher the transparency is.
実施例１〜４３
参考例で得たポリアミド酸の溶液１００部（重量部、以
下同じ）にカーボンブラック３部を加え、ミキシングロ
ールで均一に混練してペーストを得、これをガラス板上
に流延し、形成された層を熱風乾燥機中１２０℃で６０
分間、ついで１８０℃で６０分間、最後に２５０℃で６
時間加熱し、厚さ４０−の黒色ポリイミドフィルムから
なる耐熱性ベース層を得た。Examples 1 to 43 Add 3 parts of carbon black to 100 parts (by weight, the same applies hereinafter) of the polyamic acid solution obtained in the reference example, knead it uniformly with a mixing roll to obtain a paste, and pour this onto a glass plate. The formed layer was dried at 120°C for 60 minutes in a hot air dryer.
for 60 minutes at 180°C and finally at 250°C for 60 minutes.
The mixture was heated for an hour to obtain a heat-resistant base layer made of a black polyimide film with a thickness of 40 mm.
次に、同じポリアミド酸の溶液１００部にチタニア１．
２部を加えたものからなるペーストを、前記の耐熱性ベ
ース層上に流延し、前記に準じ処理してポリイミド化し
、白色の被マーキング層を形成し、全体の厚さが１００
μｍの複層柔軟基材を得た。Next, 1.0 parts of titania was added to 100 parts of the same polyamic acid solution.
A paste consisting of the above heat-resistant base layer was cast on the heat-resistant base layer, and treated as described above to form a polyimide, forming a white marking layer with a total thickness of 100 mm.
A multilayer flexible base material of μm was obtained.
ついで、前記の複層柔軟基材における黒色ポリイミド面
にシリコーン系感圧接着剤（日東電工社製、！ｌ！１３
３６）を付設しく厚さ２０μｍ） 、耐熱性表示素材を
得た。Next, a silicone pressure-sensitive adhesive (manufactured by Nitto Denko Corporation, !l!13) was applied to the black polyimide surface of the multilayer flexible base material.
36) was added to obtain a heat-resistant display material with a thickness of 20 μm).
前記の耐熱性表示素材より所定サイズのラベル基材を切
り出し、その被マーキング層にＮｄ： Ｙ ＡＧレーザ
光線（出力１５０Ｗ）を照射してエツチング処理し、所
定のバーコードパターンを形成した。A label base material of a predetermined size was cut out from the heat-resistant display material, and the marking layer was etched by irradiating it with a Nd:YAG laser beam (output 150 W) to form a predetermined barcode pattern.
そのバーコードパターンにおける黒色ナローバーの幅は
１２５部５μｍであった。また、そのペリファイヤーに
よる検証におけるＰＣ３値は８７〜９１％であり、全て
の実施例がバーコードの読み取りやすさの基準である７
５％を超えるものであった。The width of the black narrow bar in the barcode pattern was 125 parts and 5 μm. In addition, the PC3 value in verification by the perifier was 87 to 91%, and all examples were 7, which is the standard for barcode readability.
It exceeded 5%.
実施例４４
カーボンブラック５部、分子量１４００、エポキシ当量
８７５〜９７５のビスフェノールＡ型固形エポキシ樹脂
３２部、フェノール樹脂系硬化剤１，３部、２ｎ−ヘプ
タデシルイミダゾール０．５４部、ニトリル・ブタジエ
ンゴム１Ｏ０８部をロールミルで均一に混練してペース
トとし、これを厚さ３０μｌのアルミニラム箔の片面に
キャスティングし、乾燥させて厚さ４０部ｍの複層柔軟
基材を形成した。Example 44 5 parts of carbon black, 32 parts of bisphenol A solid epoxy resin with a molecular weight of 1400 and an epoxy equivalent of 875 to 975, 1.3 parts of a phenolic resin curing agent, 0.54 part of 2n-heptadecylimidazole, nitrile-butadiene rubber 1008 parts were uniformly kneaded with a roll mill to form a paste, which was cast on one side of aluminum foil with a thickness of 30 μl and dried to form a multilayer flexible base material with a thickness of 40 parts m.
一方、分子量３８０、エポキシ当量１８４〜１９４のビ
スフェノールＡ型液状エポキシ樹脂６０部、エポキシ当
量３９０〜４７０のダイマー酸変性エポキシ樹脂２０部
、ジシアンジアミド５部、Ｎ’−（３，４−ジクロロフ
ェニル）−Ｎ、Ｎ−ジメチル尿素２部をミキシングロー
ルで均一に混練し、その混合物をセパレータ間に介在さ
せて直圧式プレスにて厚さ５０−のエポキシ樹脂含有シ
ートを得、これを前記の複層柔軟基材におけるアルミニ
ウム面にセパレータを剥がして接着し、耐熱性表示素材
を得た。On the other hand, 60 parts of bisphenol A liquid epoxy resin with a molecular weight of 380 and an epoxy equivalent of 184 to 194, 20 parts of a dimer acid-modified epoxy resin with an epoxy equivalent of 390 to 470, 5 parts of dicyandiamide, N'-(3,4-dichlorophenyl)-N , 2 parts of N-dimethylurea were uniformly kneaded with a mixing roll, the mixture was interposed between separators, and a 50-thick epoxy resin-containing sheet was obtained using a direct pressure press. The separator was peeled off and adhered to the aluminum surface of the material to obtain a heat-resistant display material.
前記の耐熱性表示素材より所定サイズのラベル基材を切
り出し、その黒色被マーキング層に炭酸ガスレーザ光線
（出力８０Ｗ）を照射してエツチング処理し、所定のバ
ーコードパターンを形成した。A label base material of a predetermined size was cut out from the heat-resistant display material, and its black marking layer was etched by irradiating it with a carbon dioxide laser beam (output 80 W) to form a predetermined barcode pattern.
そのバーコードパターンにおけるアルミニウム地色のワ
イドバーの幅は３００±１２μ鴎であり、ＰＣ８値は８
２％であった。The width of the aluminum wide bar in the barcode pattern is 300±12μ, and the PC8 value is 8.
It was 2%.
第１図は本発明の耐熱性表示素材の構造例の断面図、第
２図はラベル例の断面図である。
１：被マーキング層
２：耐熱性ベース層
３：耐熱性接着層
４：パターン層
特許出願人 日東電工株式会社FIG. 1 is a sectional view of a structural example of a heat-resistant display material of the present invention, and FIG. 2 is a sectional view of an example of a label. 1: Marking layer 2: Heat-resistant base layer 3: Heat-resistant adhesive layer 4: Pattern layer Patent applicant Nitto Denko Corporation
Claims (1)
処理を受ける着色剤含有の耐熱性樹脂層からなる被マー
キング層を有する複層柔軟基材の裏面に、被着体への仮
着が可能な耐熱性接着層を有することを特徴とする耐熱
性表示素材。 ２、複層柔軟基材の波長４００〜９００ｎｍの光に対す
るＰＣＳ値が２５％以上である請求項１に記載の耐熱性
表示素材。 ３、被マーキング層がエポキシ成分含有の着色ポリイミ
ドからなる請求項１又は２に記載の耐熱性表示素材。 ４、耐熱性ベース層が金属箔からなる請求項１〜３に記
載の耐熱性表示素材。 ５、請求項１〜４に記載の耐熱性表示素材における被マ
ーキング層に、レーザー光線によるエッチングパターン
を形成してなることを特徴とするラベル。[Scope of Claims] 1. An adherend is placed on the back side of a multilayer flexible base material having a marking layer made of a colorant-containing heat-resistant resin layer that is subjected to an etching pattern formation process on a heat-resistant base layer. A heat-resistant display material characterized by having a heat-resistant adhesive layer that can be temporarily attached to. 2. The heat-resistant display material according to claim 1, wherein the multilayer flexible base material has a PCS value of 25% or more for light with a wavelength of 400 to 900 nm. 3. The heat-resistant display material according to claim 1 or 2, wherein the marking layer is made of colored polyimide containing an epoxy component. 4. The heat-resistant display material according to claim 1, wherein the heat-resistant base layer is made of metal foil. 5. A label characterized by forming an etching pattern using a laser beam on the marking layer of the heat-resistant display material according to any one of claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63272789A JP2717188B2 (en) | 1988-10-28 | 1988-10-28 | Heat resistant display materials and labels |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63272789A JP2717188B2 (en) | 1988-10-28 | 1988-10-28 | Heat resistant display materials and labels |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02120042A true JPH02120042A (en) | 1990-05-08 |
| JP2717188B2 JP2717188B2 (en) | 1998-02-18 |
Family
ID=17518767
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63272789A Expired - Lifetime JP2717188B2 (en) | 1988-10-28 | 1988-10-28 | Heat resistant display materials and labels |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2717188B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0623908A1 (en) * | 1993-05-07 | 1994-11-09 | Nitto Denko Corporation | Individual identification label |
| US5688573A (en) * | 1991-12-18 | 1997-11-18 | Minnesota Mining And Manufacturing Company | Halogen-free acrylic urethane sheet material |
| US6824849B2 (en) | 2000-08-07 | 2004-11-30 | 3M Innovative Properties Company | Laser-cuttable multi-layer sheet material |
| CN110396379A (en) * | 2019-07-16 | 2019-11-01 | 湖北锂诺新能源科技有限公司 | A kind of lithium ion battery protective glue band carrying out laser coding |
| US11795344B2 (en) | 2017-06-01 | 2023-10-24 | Lg Chem, Ltd. | Multilayer marking film |
-
1988
- 1988-10-28 JP JP63272789A patent/JP2717188B2/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5688573A (en) * | 1991-12-18 | 1997-11-18 | Minnesota Mining And Manufacturing Company | Halogen-free acrylic urethane sheet material |
| EP0623908A1 (en) * | 1993-05-07 | 1994-11-09 | Nitto Denko Corporation | Individual identification label |
| US5521034A (en) * | 1993-05-07 | 1996-05-28 | Nitto Denko Corporation | Individual identification label |
| US5562993A (en) * | 1993-05-07 | 1996-10-08 | Nitto Denko Corporation | Semiconductor device with identification information |
| US6824849B2 (en) | 2000-08-07 | 2004-11-30 | 3M Innovative Properties Company | Laser-cuttable multi-layer sheet material |
| US11795344B2 (en) | 2017-06-01 | 2023-10-24 | Lg Chem, Ltd. | Multilayer marking film |
| CN110396379A (en) * | 2019-07-16 | 2019-11-01 | 湖北锂诺新能源科技有限公司 | A kind of lithium ion battery protective glue band carrying out laser coding |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2717188B2 (en) | 1998-02-18 |
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