JPH0431498B2 - - Google Patents
Info
- Publication number
- JPH0431498B2 JPH0431498B2 JP61243218A JP24321886A JPH0431498B2 JP H0431498 B2 JPH0431498 B2 JP H0431498B2 JP 61243218 A JP61243218 A JP 61243218A JP 24321886 A JP24321886 A JP 24321886A JP H0431498 B2 JPH0431498 B2 JP H0431498B2
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- chloride resin
- layer
- resin composition
- sheet
- 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 - Lifetime
Links
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 94
- 229920005989 resin Polymers 0.000 claims description 67
- 239000011347 resin Substances 0.000 claims description 67
- 238000004049 embossing Methods 0.000 claims description 60
- 238000005187 foaming Methods 0.000 claims description 45
- 239000011342 resin composition Substances 0.000 claims description 42
- 238000006116 polymerization reaction Methods 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 18
- 238000007639 printing Methods 0.000 claims description 15
- 239000006260 foam Substances 0.000 claims description 13
- 230000001360 synchronised effect Effects 0.000 claims description 11
- 239000004088 foaming agent Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 description 26
- 238000010438 heat treatment Methods 0.000 description 20
- 239000004014 plasticizer Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 229920003002 synthetic resin Polymers 0.000 description 8
- 239000000057 synthetic resin Substances 0.000 description 8
- 230000006378 damage Effects 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- 239000004604 Blowing Agent Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 210000000497 foam cell Anatomy 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000002023 wood Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000005323 electroforming Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 239000004156 Azodicarbonamide Substances 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 4
- 235000019399 azodicarbonamide Nutrition 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- -1 maleic acid ester Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000003429 antifungal agent Substances 0.000 description 3
- 229940121375 antifungal agent Drugs 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 239000000417 fungicide Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- KCXZNSGUUQJJTR-UHFFFAOYSA-N Di-n-hexyl phthalate Chemical compound CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCC KCXZNSGUUQJJTR-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229910052570 clay Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000009408 flooring Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000007646 gravure printing Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 2
- XMNDMAQKWSQVOV-UHFFFAOYSA-N (2-methylphenyl) diphenyl phosphate Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 XMNDMAQKWSQVOV-UHFFFAOYSA-N 0.000 description 1
- VCRZAKVGPJFABU-UHFFFAOYSA-N 10-phenoxarsinin-10-yloxyphenoxarsinine Chemical group C12=CC=CC=C2OC2=CC=CC=C2[As]1O[As]1C2=CC=CC=C2OC2=CC=CC=C21 VCRZAKVGPJFABU-UHFFFAOYSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- NCDBYAPSWOPDRN-UHFFFAOYSA-N 2-[dichloro(fluoro)methyl]sulfanylisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(SC(Cl)(Cl)F)C(=O)C2=C1 NCDBYAPSWOPDRN-UHFFFAOYSA-N 0.000 description 1
- ALKCLFLTXBBMMP-UHFFFAOYSA-N 3,7-dimethylocta-1,6-dien-3-yl hexanoate Chemical compound CCCCCC(=O)OC(C)(C=C)CCC=C(C)C ALKCLFLTXBBMMP-UHFFFAOYSA-N 0.000 description 1
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 1
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-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
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- YYQRGCZGSFRBAM-UHFFFAOYSA-N Triclofos Chemical compound OP(O)(=O)OCC(Cl)(Cl)Cl YYQRGCZGSFRBAM-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- QBLDFAIABQKINO-UHFFFAOYSA-N barium borate Chemical compound [Ba+2].[O-]B=O.[O-]B=O QBLDFAIABQKINO-UHFFFAOYSA-N 0.000 description 1
- SHLNMHIRQGRGOL-UHFFFAOYSA-N barium zinc Chemical compound [Zn].[Ba] SHLNMHIRQGRGOL-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 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
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002666 chemical blowing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- PUFGCEQWYLJYNJ-UHFFFAOYSA-N didodecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCCC PUFGCEQWYLJYNJ-UHFFFAOYSA-N 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical class CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 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 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011490 mineral wool Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000010022 rotary screen printing Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 229960001147 triclofos Drugs 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000005335 volcanic glass Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Shaping Of Tube Ends By Bending Or Straightening (AREA)
Description
〔産業上の利用分野〕
本発明は、床材、壁材などの建築材料ならびに
車両用シート、靴、袋物、家具などに使用され
る、印刷意匠と凹凸意匠とが一致し、かつシート
表面に繊細でシヤープな絞意匠を有する装飾性に
優れた同調エンボスシートの製造方法に関する。
〔従来の技術〕
従来、印刷意匠と凹凸意匠とを一致させた同調
エンボスシートの製造方法としては、発泡性合成
樹脂層の表面に、発泡抑制剤および／または発泡
促進剤を含む印刷インクを印刷して印刷インク層
を積層し、そののち、この発泡性合成樹脂層を発
泡させてシート表面に凹凸意匠を発現させるケミ
カルエンボス加工と、エンボスロールを使用して
シートの印刷意匠に合わせてエンボス加工を施す
メカニカルエンボス加工とがある。
〔発明が解決しようとする問題点〕
ところで、前者のケミカルエンボス加工の場合
は、シートの印刷意匠と凹凸意匠とを一致させる
ことはできるが、凹凸の境界がはつきりしないた
め、繊細でシヤープな凹凸表現は不可能であり、
また後者のメカニカルエンボス加工の場合は、使
用するエンボスロールの形状により、シート面へ
の繊細でシヤープな凹凸表現は可能であるが、印
刷意匠と凹凸意匠とを機械的に合わせるため、シ
ートの伸縮や機械条件などにより両意匠を合わせ
難く、非常に作業性が悪いとともに、不良品の発
生が多かつた。
本発明は、このような従来技術の問題点に鑑み
なされたもので、シートの印刷意匠とケミカルエ
ンボス加工によるシートの凹凸意匠とを一致さ
せ、かつこのケミカルエンボス加工により隆起し
たシート表面に繊細でシヤープな絞意匠の現出を
可能にした同調エンボスシートの製造方法を提供
することを目的とする。
〔問題を解決するための手段〕
本発明は、シート基材に、順次、発泡剤を含有
する発泡性塩化ビニル系樹脂組成物層と、発泡促
進剤を含む印刷インクよりなる柄模様状の印刷イ
ンク層と、透明もしくは半透明の塩化ビニル系樹
脂層とを積層して積層シートを形成し、そののち
該積層シートを加熱して前記発泡性塩化ビニル系
樹脂組成物層を発泡させて凹凸模様を現出せし
め、次いでその表面に任意の形状の意匠をロール
周面に刻設したエンボスロールにより絞模様を形
成し、印刷模様と凹凸模様とが一致した同調エン
ボスシートを製造する方法において、前記発泡性
塩化ビニル系樹脂組成物層に使用される塩化ビニ
ル系樹脂の平均重合度を1200以上、かつ透明もし
くは半透明の塩化ビニル系樹脂層に使用される塩
化ビニル系樹脂の平均重合度を前記発泡性塩化ビ
ニル系樹脂組成物層の平均重合度より100以上高
いものとなし、しかも発泡性塩化ビニル系樹脂組
成物層の発泡倍率を４倍以下としたことを特徴と
する同調エンボスシートの製造方法を提供するも
のである。
以下、本発明を詳細に説明すると、前記シート
基材の材質としては、一般にシート基材として使
用されている、例えば天然の動物性または植物性
繊維、アスベスト、ガラス繊維、ロツクウール、
パルプ、合成樹脂繊維などの無機または有機繊維
を、単独もしくは適宜混合し、かつ必要に応じて
炭酸カルシウム、クレー、水酸化アルミニウムな
どの充填剤や樹脂バインダーを混合した織布、不
織布、編布、紙などの離型性担体が使用でき、こ
れらは、目的とする製品の用途に応じて自由に使
い分けることができる。
また、このシート基材としては、合成樹脂の発
泡シートまたは非発泡シートを前記シート基材の
床面側に積層したものも使用できる。
さらに、このシート基材の厚みとしては、通
常、0.1〜２mmが好ましく、0.1mm未満では得られ
るシートの強度が弱くなる一方、２mmを超えると
コスト高となり経済的でない。
前記発泡性塩化ビニル系樹脂組成物層の主成分
は、塩化ビニル系樹脂および加熱により分解して
ガスを発生する化学発泡剤などを含有するが、そ
のほか必要に応じて、可塑剤、発泡剤の分解を促
進しない安定剤、充填剤、防黴剤、粘度低下剤、
および着色剤などの添加剤が使用される。
また、ここでいう塩化ビニル系樹脂とは、ポリ
塩化ビニル樹脂、および塩化ビニルと他のモノマ
ー、例えばエチレン、酢酸ビニル、ビニルエーテ
ル、マレイン酸エステル、（メタ）アクリル酸、
（メタ）アクリル酸エステルなどとの共重合体の
ほか、ポリ塩化ビニル樹脂と他のポリマーとの混
合物も含むものであり、使用する塩化ビニル系樹
脂の平均重合度は1200以上、好ましくは1200〜
3000であることが必要であり、平均重合度が1200
未満であると、加熱しつつメカニカルエンボスを
施す際に、発泡性塩化ビニル系樹脂組成物層の溶
融粘度が低くなり、エンボスロールの押圧で発泡
セルの破壊による表面荒れを生じ、エンボス加工
が難しくなる。
なお、本発明において使用する平均重合度と
は、一般に市場に供給される塩化ビニル系樹脂の
重合度を示すものであり、重合度の比較的大きな
ものと比較的小さいなものとが混在する、かかる
樹脂中の個々の分子の重合度を平均したものであ
る。
そして、本発明においては、使用する塩化ビニ
ル系樹脂が１種類のものであれば、その樹脂の平
均重合度を意味し、平均重合度の異なる複数種の
樹脂のブレンド使用であれば、後記する実施例に
みられるように各樹脂の配合割合を加味しての算
術平均を意味するものである。
前記発泡性塩化ビニル系樹脂組成物層に含有さ
れる発泡剤としては、例えばアゾジカルボンアミ
ド、ジニトロソペンタメチレンテトラミンなどの
通常のものが使用できるが、中でもアゾジカルボ
ンアミドが好ましく、またその添加量は、塩化ビ
ニル系樹脂100重量部に対し、0.5〜５重量部が好
ましく、0.5重量部未満では発泡が充分に生起せ
ず、一方５重量部を超えると発泡倍率を４倍以下
に調整することが難しく、好ましくない。
前記可塑剤としては、ジブチルフタレート、ジ
イソブチルフタレート、ジオクチルフタレート、
ジドデシルフタレート、ブチルベンジルフタレー
ト、ジイソデシルフタレート、ジヘキシルフタレ
ート、ジイソノニルフタレート、ジオクチルアジ
ペート、ジイソデシルアジペート、ジブチルセバ
ケート、ジオクチルセバケート、トリブチルホス
フエート、トリクレジルホスフエート、トリフエ
ニルホスフエート、トリクロルエチルホスフエー
ト、トリオクチルホスフエート、ジフエニルクレ
ジルホスフエートなどのほか、トリメリツト酸エ
ステル系可塑剤、エポキシ化大豆油や、各種エポ
キシ樹脂などのエポキシ系可塑剤、ポリエステル
系高分子可塑剤などが使用できる。
なお、塩化ビニル系樹脂ペーストを使用する場
合には、粘度低下を目的として、粘度低下剤、ガ
ソリン、オクタン、ベンゼン、トルエン、ナフ
サ、ドデシルベンゼン誘導体などの希釈剤もしく
は二次可塑剤などが可塑剤と併用される。
この場合、塩化ビニル系樹脂100重量部に対し
て、可塑剤の添加量は20〜100重量部、また粘度
低下剤は0.1〜５重量部、希釈剤および二次可塑
剤は１〜20重量部の範囲が好ましい。
前記発泡剤の分解を促進する作用のない安定剤
としては、使用する発泡剤の種類に応じ選定する
ことが必要であるが、発泡剤としてアゾジカルボ
ンアミドを使用する場合は、スズ系、バリウム
系、カルシウム系、バリウム−亜鉛系で亜鉛含有
量の低いもの、カルシウム−亜鉛系で亜鉛含有量
の低いものなどの使用が必要である。
この安定剤の添加量は、塩化ビニル系樹脂100
重量部に対して、0.5〜７重量部の範囲が好まし
く、0.5重量部未満では塩化ビニル系樹脂の熱安
定性が悪くなり、一方７重量部を超えるとブリー
ド、ブルームなどの品質上の問題を起こし易くな
るばかりでなく、価格が高くなり好ましくない。
前記充填剤としては、加工温度にて溶解、分解
などの物理的、化学的は変化をしないものであれ
ばどんな充填剤でもよいが、炭酸カルシウム、炭
酸マグネシウム、クレー、タルク、シリカ、ケイ
藻土、ケイ砂、軽石粉、雲母粉、アベスト、水酸
化アルミニウム、酸化アルミニウム、硫酸アルミ
ニウム、硫酸バリウム、硫酸カルシウム、ガラス
球、発泡ガラス球、フライアツシユ球、火山ガラ
ス中空体（シラスバルーン）などの無機質充填
剤、粉末繊維系（セルロウースパウダー）、ポリ
ビニルアルコール繊維、コルク粉末、木粉、熱硬
化性樹脂粉末、熱硬化性樹脂中空球などの有機質
充填剤などが使用できる。
この充填剤の添加量は、塩化ビニル系樹脂100
重量部に対し、５〜400重量部の範囲が好ましい。
前記防黴剤としては、変色させたり、発泡促進
剤に対する発泡促進効果を阻害したりすることの
ない10，10′−オキシビスフエノキシアルシン、
Ｎ−（フルオロジクロロメチルチオ）−フタルイミ
ド、Ｎ−トリクロロメチルメルカプト−４−シク
ロヘキサン−１・２−ジカルボキシイミド、２，
４，５，６−テトラクロロイソフタロニトリルな
どの有機系防黴剤を塩化ビニル系樹脂100重量部
に対し0.1〜５重量部、効果持続性が要求される
場合には、メタホウ酸バリウムなどの無機系防黴
剤を１〜30重量部併用するのが好ましい。
なお、この防黴剤は、単独でも２種以上を混合
しても使用できるものである。
前記印刷インク層に使用される印刷インクの種
類は特に限定されないが、印刷インクの少なくと
も一部には、必ず発泡剤を含有する塩化ビニル系
樹脂組成物の発泡を促進し、凸部を形成するため
の発泡促進剤を配合することが必要である。
この発泡促進剤としては、使用する発泡剤の種
類に応じて選択することが必要であるが、例えば
発泡剤として、アゾジカルボンアミドを使用する
場合は、オクチル酸亜鉛、ナフテン酸亜鉛、酸化
亜鉛、ステアリン酸亜鉛、安息香酸、亜鉛などの
亜鉛化合物、尿素化合物、ｐ−トルエンスルホニ
ルヒドラジド、Ｐ，P′−オキシビスベンゼンスル
ホンニルヒドラジドなどのヒドラジド化合物など
の発泡促進剤が使用できる。
なお、この発泡促進剤の添加量は、目的とする
凸部の高さに応じて調節されるが、印刷インク
100重量部に対し１〜50重量部の範囲が好ましく、
１重量部未満では発泡が充分でなく、一方50重量
部を超えると発泡セルが粗くなり、後工程のエン
ボスの際、セル破壊による表面肌荒れを起こし易
く好ましくない。
前記透明もしくは半透明の塩化ビニル系樹脂層
としては、前記発泡性塩化ビニル系樹脂組成物層
に使用される塩化ビニル系樹脂が使用できる。こ
の透明もしくは半透明の塩化ビニル系樹脂層を構
成する塩化ビニル系樹脂の平均重合度は、前記発
泡性塩化ビニル系樹脂組成物層の塩化ビニル系樹
脂より100以上、好ましくは100〜4000高いことが
必要である。エンボスロールによりエンボス模様
の再現性（エンボス適性）および発泡促進剤によ
る発泡促進効果の点からは、使用する塩化ビニル
系樹脂の平均重合度が低い方が樹脂の加熱溶融粘
度が低くなり加工性に富むため好ましいのである
が、後記する比較例２にも明らかなように、発泡
性塩化ビニル系樹脂組成物中の該樹脂の平均重合
度より低いと、発泡時に発泡剤の分解ガスの影響
による透明もしくは半透明の塩化ビニル系樹脂層
と発泡性塩化ビニル系樹脂組成物層との界面（す
なわち印刷面）への著しい気泡発生のため、鮮明
な印刷模様が得られない。また、上記比較例２、
後記する実施例からも把握されるように、表面平
滑性を良好ならしめるという点からも透明もしく
は半透明の塩化ビニル系樹脂層に使用する塩化ビ
ニル系樹脂の平均重合度は発泡性塩化ビニル系樹
脂組成物層に使用される塩化ビニル系樹脂の平均
重合度よりも100以上高いことが要求される。な
お、塩化ビニル系樹脂の平均重合度が高くなる
と、樹脂の加熱溶融粘度が高くなり加工性に劣る
ため、エンボス適性ならびに発泡促進効果を引き
出すことを考慮すると4000以下が好ましい。
なお、この透明もしくは半透明の塩化ビニル系
樹脂層には、必要に応じて可塑剤、安定剤、充填
剤または艶消剤、防黴剤、粘度低下剤、着色剤な
どの添加剤が使用できる。
また、この透明もしくは半透明の塩化ビニル系
樹脂層に使用される塩化ビニル系樹脂および添加
剤は、前記したように、発泡性塩化ビニル径樹脂
組成物層に使用されるものが、例えば同一配合量
で使用できるが、ただし前記充填剤または艶消剤
の場合は、塩化ビニル系樹脂100重量部に対して
0.5〜20重量部とするのが好ましく、この配合量
が20重量部を越えると透明もしくは半透明の塩化
ビニル系樹脂層が不透明となる。
さらに、本発明においては、前記発泡性塩化ビ
ニル系樹脂組成物層の発泡倍率は、４倍以下、好
ましくは1.4〜４倍にする必要があり、４倍を超
えるとメカニカルエンボス加工の際に、発泡層の
セル破壊が起こり好ましくない。
なお、発泡倍率とは、この種の技術で一般に使
用される発泡倍率と同じである。すなわち、シー
ト基材上に形成する発泡性塩化ビニル系樹脂組成
物層の厚みを基準とし、これを加熱発泡させたの
ちの発泡層の厚みが元の何倍になるかで表すもの
である。
本発明の同調エンボスシートは、前記シート基
材に発泡性塩化ビニル系樹脂組成物層をカレンダ
ー法、押出法、ラミネート法、ペーストコーテイ
ング法などの方法で形成し、その表面にグラビア
印刷法、フレキソ印刷法、ロータリースクリーン
印刷法、シルクスクリーン印刷法などの方法で任
意意匠を印刷し、この任意意匠を印刷した発泡性
塩化ビニル系樹脂組成物層の表面に、カレンダー
法、押出法、ラミネート法、ペーストコーテイン
グ法などの方法で透明もしくは半透明の塩化ビニ
ル系樹脂層を形成したのち、発泡促進剤を含む印
刷インク層が形成された部分に対応する発泡性塩
化ビニル系樹脂組成物層中の発泡剤の分解温度以
上（好ましくは発泡促進剤を含まない印刷部に対
応する発泡性塩化ビニル系樹脂組成物層中の発泡
剤の分解温度以下）で発泡性塩化ビニル系樹脂組
成物層を加熱発泡して印刷意匠と凹凸意匠とが一
致した積層シートを形成し、そののち任意の絞模
様を施したエンボスロールを使用して加熱エンボ
ス（メカニカルエンボス加工）を行うことにより
得られるものである。
このエンボス方法としては、発泡炉とエンボス
装置が別に設置された工程に従い、まず発泡炉で
加熱発泡（ケミカルエンボス加工）したのち、再
加熱しメカニカルエンボスを行う方法（オフライ
ン）と、発泡炉の直後にエンボス装置が設置され
た装置を用い、発泡（ケミカルエンボス加工）直
後に、加熱しメカニカルエンボス加工を行う方法
（インライン）の２通りがあるが、何れの方法で
も適用可能である。
オフラインでエンボス加工を行う場合には、形
成された発泡性塩化ビニル系樹脂組成物層が完全
に冷却されているために、エンボスロールの押圧
で発泡セルが破壊されず、シート表面の表面荒れ
の発生はないが、発泡性塩化ビニル系樹脂組成物
層に残留している未分解の発泡剤が分解し、これ
が二次発泡して発泡セルの破壊を生じることのな
い加熱条件を適用することが必要であり、一方イ
ンラインにより加熱発泡の直後にメカニカルエン
ボス加工を行う場合には、発泡性塩化ビニル系樹
脂組成物層が軟化状態であるため、できるだけシ
ート裏面を冷却し、表面を発泡性塩化ビニル系樹
脂組成物層に残留する未分解の発泡剤が２次発泡
しない条件で加熱してメカニカルエンボス加工を
行うことが必要となる。
また、メカニカルエンボス加工時に、エンボス
ロールとラバーロール（バツクアツプロール）と
の間に間隙を設けた、いわゆるクリアランスエン
ボスを行うことは、発泡層の発泡セル破壊を防止
する意味で有効である。この場合のクリアンラス
（間隙）は、発泡層の発泡倍率と発泡層を形成す
る塩化ビニル系樹脂の平均重合度により多少変化
するため、おのおのについて確認したうえで設定
することが必要である。例えば、発泡層の発泡倍
率が2.5倍以下で、発泡層を形成する熱可塑性合
成樹脂の平均重合度が1200以上で、かつ発泡層が
２次発泡しない程度の加熱条件で加熱し、エンボ
スロールの押圧が２〜３Kg／cm2（ゲージ圧）でメ
カニカルエンボス加工することにより、前記のよ
うなクリアランスを設けなくても発泡セルの破壊
などのない、目的とする同調エンボスシートが容
易に得られる。発泡層の発泡倍率が2.5倍を超え
る場合には、発泡倍率が高くなうに従い、クリア
ランスを設けることが好ましい。
さらに、このメカニカルエンボス加工時に使用
するシート加熱用のヒータは、例えば電気ヒー
タ、赤外線もしくは遠赤外線ヒータ、セラミツク
ヒータなどが好ましい。
また、このエンボスロールは、シート表面に任
意の絞模様を形成するための意匠をミル押しで形
成したもの、腐蝕（エツチング）により形成した
もの、電鋳法により形成したもの、シリコン樹脂
などの耐熱性合成樹脂にシート表面に任意の絞模
様を形成するための意匠を形成したものなど、い
ずれのものも使用できるが、なかでも自然の材料
からそのままの表面形状を発現可能な点で電鋳方
式のエンボスロール、シリコンなどの合成樹脂製
エンボスロールが好ましく、また耐久性、形状保
持性（温度変化による寸法変化や形状変化が少な
い）および冷却可能な点から電鋳方式のエンボス
ロールが好ましい。
〔作用〕
本発明は、シート基材の表面に発泡性塩化ビニ
ル系樹脂組成物層を形成し、その表面に発泡促進
剤を含む印刷インクで任意の柄模様を印刷し、そ
の上に透明もしくは半透明の塩化ビニル系樹脂層
を積層して積層シートを形成し、次にこの積層シ
ートを加熱して前記発泡性塩化ビニル系樹脂組成
物層を発泡させて凹凸模様を現出せしめ、そのの
ち任意形状の意匠をロール周面に刻設したエンボ
スロールを使用して加熱エンボス方式により、前
記発泡により隆起したシート表面に、絞意匠を形
成するメカニカルエンボス加工を施すことによ
り、印刷意匠と凹凸意匠とが一致し、かつその表
面に繊細でシヤープな絞意匠が形成された意匠性
に富む同調エンボスシートを容易にかつ経済的に
製造することができる。
また、発泡性塩化ビニル系樹脂組成物層に使用
する塩化ビニル系樹脂の平均重合度は1200以上で
あり、さらに透明もしくは半透明の塩化ビニル系
樹脂層に使用する合成樹脂の平均重合度は、前記
発泡性塩化ビニル系樹脂組成物層のものの平均重
合度より100以上高いものであり、さらにまた発
泡性塩化ビニル系樹脂組成物層の発泡倍率を４倍
以下とすることにより、エンボスロールを使用し
てのエンボス加工の際に加熱されて軟化もしくは
溶融状態にある発泡性塩化ビニル系樹脂組成物層
のエンボスロールの押圧による発泡セル破壊とシ
ートの表面の肌荒れなどの支障がなく、目的とす
る同調エンボスシートを容易に製造することがで
きる。
さらに、本発明は、印刷インク層を多色の印刷
インク層にすることで、複雑で繊細な装飾性に優
れたシートが得られ、これは、床材、壁材などの
建築材料、車両用シート、靴、袋物、家具などへ
の使用に適したものである。
〔実施例〕
以下、本発明の実施例を詳細に説明する。
実施例１〜２、比較例１
本実施例の同調エンボスシートの製造方法は、
まず、有効機械幅450mmのテストコーターを使用
し、ガラス繊維、パルブ、無機質填料およびバイ
ンダを主成分とする0.95mmの厚さの無機填料紙の
表面に、第１表に記載する発泡剤を含む塩化ビニ
ル樹脂ペースト（）〜（）をドクターナイフ
で各々0.45mmの厚みになるように塗布し、これ
を、170℃に設定した加熱炉に２ｍ／分の速度で
通過させ、この塩化ビニル樹脂ペースト（）〜
（）を加熱してゲル化した。
この表面に木板の板継目の目地を残して発泡促
進剤であるオクチル酸亜鉛10重量％を含む印刷イ
ンクで印刷し、その表面に通常のインクを使用し
て木目や目地の印刷を行い、そののち第１表に記
載した透明性塩化ビニル樹脂ペースト（）をド
クターナイフにて0.3mmの厚さとなるように塗布
し、170℃に設定した加熱炉を２ｍ／分の速度で
通過させ、この透明性塩化ビニル樹脂ペースト
（）をゲル化した。
そののち、190℃に設定した加熱炉を1.0〜1.4
ｍ／分の速度で通過させ、発泡直後の総厚を2.0
〜2.2mmとし、加熱直後にインラインで設置され
ているエンボス装置で、天然木そのままの木目意
匠を付した電気ヒータを内蔵する電鋳方式のエン
ボスロールを使用して発泡性塩化ビニル系樹脂組
成物層が２次発泡しない程度の温度に加熱してエ
ンボス加工を行つた（エンボスロールとバツクア
ツプロールとのクリアランスを1.8mmに設定、エ
ンボスロースの押圧；２Kg／cm2Ｇ）。
その結果を第２表に示す。
第２表からも明らかのように、発泡性塩化ビニ
ル樹脂ペースト組成物に使用する塩化ビニル樹脂
の平均重合度が1210、1455の配合では、適性なエ
ンボス加工条件の設定により問題なく加工作業が
可能であり、得られた同調エンボスシートは、天
然木に類似した繊細な相意匠を有し、床材とし
て、好適であつた。
[Industrial Application Field] The present invention is used for building materials such as flooring and wall materials, as well as vehicle seats, shoes, bags, furniture, etc., where the printed design and the uneven design match and the sheet surface has a The present invention relates to a method for manufacturing a coordinated embossed sheet with excellent decorativeness and a delicate and sharp drawing design. [Prior Art] Conventionally, a method for producing a synchronized embossed sheet with a printed design and an uneven design is to print a printing ink containing a foaming suppressor and/or a foaming accelerator on the surface of a foamable synthetic resin layer. Then, the foamable synthetic resin layer is foamed to create an uneven design on the sheet surface, followed by chemical embossing using an embossing roll to match the printed design on the sheet. There is also a mechanical embossing process. [Problem to be solved by the invention] By the way, in the case of the former chemical embossing, it is possible to match the printed design of the sheet with the uneven design, but since the boundaries of the unevenness are not sharp, it is delicate and sharp. It is impossible to express unevenness,
In the latter case, mechanical embossing, depending on the shape of the embossing roll used, it is possible to express delicate and sharp unevenness on the sheet surface, but since the printed design and the uneven design are mechanically matched, the sheet can expand and contract. It was difficult to match the two designs due to machine conditions and other factors, resulting in very poor workability and a high incidence of defective products. The present invention has been made in view of the problems of the prior art, and is designed to match the printed design of the sheet with the uneven design of the sheet formed by chemical embossing, and to add delicate details to the surface of the sheet raised by chemical embossing. The purpose of the present invention is to provide a method for manufacturing a synchronized embossed sheet that enables the appearance of a sharp shibori design. [Means for Solving the Problems] The present invention involves printing a pattern pattern on a sheet base material, which is made of a layer of a foamable vinyl chloride resin composition containing a foaming agent and a printing ink containing a foaming accelerator. An ink layer and a transparent or translucent vinyl chloride resin layer are laminated to form a laminate sheet, and then the laminate sheet is heated to foam the foamable vinyl chloride resin composition layer to form an uneven pattern. is made to appear, and then a squeeze pattern is formed on the surface of the embossing roll with a design of an arbitrary shape engraved on the roll periphery, and the method for manufacturing a synchronized embossed sheet in which the printed pattern and the uneven pattern match, The average degree of polymerization of the vinyl chloride resin used in the foamable vinyl chloride resin composition layer is 1200 or more, and the average degree of polymerization of the vinyl chloride resin used in the transparent or translucent vinyl chloride resin layer is the same as above. Production of a synchronized embossed sheet, characterized in that the degree of polymerization is 100 or more higher than the average polymerization degree of the foamable vinyl chloride resin composition layer, and the expansion ratio of the foamable vinyl chloride resin composition layer is 4 times or less. The present invention provides a method. Hereinafter, the present invention will be described in detail. Materials for the sheet base material include natural animal or vegetable fibers, asbestos, glass fiber, rock wool, etc., which are generally used as sheet base materials.
Woven fabrics, non-woven fabrics, knitted fabrics made of inorganic or organic fibers such as pulp and synthetic resin fibers alone or mixed as appropriate, and if necessary, fillers such as calcium carbonate, clay, aluminum hydroxide, and resin binders. A releasable carrier such as paper can be used, and these can be used freely depending on the intended use of the product. Further, as this sheet base material, a foamed sheet or a non-foamed synthetic resin sheet laminated on the floor surface side of the sheet base material can also be used. Further, the thickness of the sheet base material is usually preferably 0.1 to 2 mm; if it is less than 0.1 mm, the strength of the obtained sheet will be weak, while if it exceeds 2 mm, the cost will increase and it is not economical. The main components of the foamable vinyl chloride-based resin composition layer include a vinyl chloride-based resin and a chemical blowing agent that decomposes upon heating to generate gas. Stabilizers, fillers, fungicides, viscosity reducers that do not promote decomposition,
and additives such as colorants are used. In addition, the vinyl chloride resin mentioned here refers to polyvinyl chloride resin, vinyl chloride and other monomers, such as ethylene, vinyl acetate, vinyl ether, maleic acid ester, (meth)acrylic acid,
In addition to copolymers with (meth)acrylic acid esters, it also includes mixtures of polyvinyl chloride resins and other polymers, and the average degree of polymerization of the vinyl chloride resin used is 1200 or more, preferably 1200-1200.
3000, and the average degree of polymerization is 1200.
If it is less than that, when performing mechanical embossing while heating, the melt viscosity of the foamable vinyl chloride resin composition layer will be low, and the surface will be rough due to destruction of foam cells by the pressure of the embossing roll, making embossing difficult. Become. Note that the average degree of polymerization used in the present invention indicates the degree of polymerization of vinyl chloride resins generally supplied on the market, and those with relatively high degrees of polymerization and those with relatively low degrees of polymerization coexist. It is the average degree of polymerization of individual molecules in such a resin. In the present invention, if the vinyl chloride resin used is one type, it means the average degree of polymerization of that resin, and if a blend of multiple types of resins with different average degrees of polymerization is used, it will be described later. As shown in the examples, it means the arithmetic mean taking into consideration the blending ratio of each resin. As the foaming agent contained in the foamable vinyl chloride resin composition layer, usual ones such as azodicarbonamide and dinitrosopentamethylenetetramine can be used, and among them, azodicarbonamide is preferable, and the amount added is is preferably 0.5 to 5 parts by weight per 100 parts by weight of the vinyl chloride resin; if it is less than 0.5 parts by weight, sufficient foaming will not occur, while if it exceeds 5 parts by weight, the expansion ratio should be adjusted to 4 times or less. is difficult and undesirable. The plasticizers include dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate,
Didodecyl phthalate, butylbenzyl phthalate, diisodecyl phthalate, dihexyl phthalate, diisononyl phthalate, dioctyl adipate, diisodecyl adipate, dibutyl sebacate, dioctyl sebacate, tributyl phosphate, tricresyl phosphate, triphenyl phosphate, trichloroethyl phosphate , trioctyl phosphate, diphenyl cresyl phosphate, etc., trimellitic acid ester plasticizers, epoxy plasticizers such as epoxidized soybean oil, various epoxy resins, polyester polymer plasticizers, etc. can be used. When using vinyl chloride resin paste, in order to reduce the viscosity, viscosity reducing agents, diluents such as gasoline, octane, benzene, toluene, naphtha, dodecylbenzene derivatives, or secondary plasticizers are used as plasticizers. used in conjunction with In this case, the amount of plasticizer added is 20 to 100 parts by weight, the viscosity reducing agent is 0.1 to 5 parts by weight, and the diluent and secondary plasticizer are 1 to 20 parts by weight, relative to 100 parts by weight of the vinyl chloride resin. A range of is preferred. It is necessary to select a stabilizer that does not have the effect of promoting the decomposition of the blowing agent according to the type of blowing agent used, but when using azodicarbonamide as a blowing agent, tin-based or barium-based stabilizers are used. It is necessary to use a calcium-based material, a barium-zinc-based material with a low zinc content, a calcium-zinc-based material with a low zinc content, etc. The amount of this stabilizer added is 100% of vinyl chloride resin.
It is preferably in the range of 0.5 to 7 parts by weight. If it is less than 0.5 parts by weight, the thermal stability of the vinyl chloride resin will deteriorate, while if it exceeds 7 parts by weight, quality problems such as bleeding and blooming may occur. Not only is this more likely to occur, but it also increases the cost, which is undesirable. The filler may be any filler as long as it does not undergo physical or chemical changes such as dissolution or decomposition at the processing temperature, but examples include calcium carbonate, magnesium carbonate, clay, talc, silica, and diatomaceous earth. Inorganic fillings such as silica sand, pumice powder, mica powder, abestos, aluminum hydroxide, aluminum oxide, aluminum sulfate, barium sulfate, calcium sulfate, glass bulbs, foamed glass bulbs, fly ash bulbs, volcanic glass hollow bodies (shirasu balloons), etc. Organic fillers such as powder, fiber powder (cellulose powder), polyvinyl alcohol fiber, cork powder, wood flour, thermosetting resin powder, and thermosetting resin hollow spheres can be used. The amount of this filler added is 100% of vinyl chloride resin.
The range is preferably 5 to 400 parts by weight. The antifungal agent is 10,10'-oxybisphenoxyarsine, which does not cause discoloration or inhibit the foaming promoting effect of the foaming promoter;
N-(fluorodichloromethylthio)-phthalimide, N-trichloromethylmercapto-4-cyclohexane-1,2-dicarboximide, 2,
Add 0.1 to 5 parts by weight of an organic fungicide such as 4,5,6-tetrachloroisophthalonitrile to 100 parts by weight of vinyl chloride resin, and if long-lasting effect is required, add barium metaborate or the like. It is preferable to use 1 to 30 parts by weight of an inorganic antifungal agent. In addition, this antifungal agent can be used alone or in combination of two or more kinds. The type of printing ink used in the printing ink layer is not particularly limited, but at least a portion of the printing ink must contain a foaming agent to promote foaming of the vinyl chloride resin composition and form convex portions. It is necessary to incorporate a foaming accelerator for this purpose. The foaming accelerator must be selected depending on the type of foaming agent used. For example, when azodicarbonamide is used as the foaming agent, zinc octylate, zinc naphthenate, zinc oxide, Foaming promoters such as zinc compounds such as zinc stearate, benzoic acid, and zinc, urea compounds, and hydrazide compounds such as p-toluenesulfonyl hydrazide and P,P'-oxybisbenzenesulfonyl hydrazide can be used. The amount of foaming accelerator added is adjusted depending on the desired height of the convex portion, but
The range is preferably 1 to 50 parts by weight per 100 parts by weight,
If it is less than 1 part by weight, foaming will not be sufficient, while if it exceeds 50 parts by weight, the foamed cells will become rough and the surface will be likely to become rough due to cell destruction during embossing in the subsequent process, which is not preferable. As the transparent or translucent vinyl chloride resin layer, the vinyl chloride resin used in the foamable vinyl chloride resin composition layer can be used. The average degree of polymerization of the vinyl chloride resin constituting this transparent or translucent vinyl chloride resin layer is 100 or more, preferably 100 to 4000 higher than the vinyl chloride resin of the foamable vinyl chloride resin composition layer. is necessary. In terms of the reproducibility of the embossed pattern (embossing suitability) with the embossing roll and the foaming promotion effect of the foaming accelerator, the lower the average degree of polymerization of the vinyl chloride resin used, the lower the heated melt viscosity of the resin, which improves processability. However, as is clear from Comparative Example 2, which will be described later, if the degree of polymerization is lower than the average degree of polymerization of the resin in the foamable vinyl chloride resin composition, transparency may decrease due to the influence of the decomposed gas of the blowing agent during foaming. Alternatively, a clear printed pattern cannot be obtained due to the generation of significant air bubbles at the interface (ie, printing surface) between the translucent vinyl chloride resin layer and the foamable vinyl chloride resin composition layer. In addition, the above comparative example 2,
As will be understood from the examples below, the average degree of polymerization of the vinyl chloride resin used for the transparent or semitransparent vinyl chloride resin layer is higher than that of the foamable vinyl chloride resin in order to improve the surface smoothness. The polymerization degree is required to be 100 or more higher than the average polymerization degree of the vinyl chloride resin used in the resin composition layer. Note that when the average degree of polymerization of the vinyl chloride resin becomes high, the heat-melt viscosity of the resin increases and the processability becomes poor, so it is preferably 4000 or less in order to bring out embossing suitability and foaming promotion effect. In addition, additives such as plasticizers, stabilizers, fillers, matting agents, fungicides, viscosity reducers, colorants, etc. can be used in this transparent or translucent vinyl chloride resin layer as necessary. . In addition, as mentioned above, the vinyl chloride resin and additives used in this transparent or translucent vinyl chloride resin layer may have the same composition as those used in the expandable vinyl chloride diameter resin composition layer. However, in the case of the above-mentioned fillers or matting agents, it can be used in amounts per 100 parts by weight of vinyl chloride resin.
The amount is preferably 0.5 to 20 parts by weight, and if this amount exceeds 20 parts by weight, the transparent or translucent vinyl chloride resin layer becomes opaque. Furthermore, in the present invention, the foaming ratio of the foamable vinyl chloride resin composition layer needs to be 4 times or less, preferably 1.4 to 4 times, and if it exceeds 4 times, during mechanical embossing, Cell destruction of the foam layer occurs, which is undesirable. Note that the foaming ratio is the same as the foaming ratio generally used in this type of technology. That is, based on the thickness of the foamable vinyl chloride resin composition layer formed on the sheet base material, it is expressed as how many times the original thickness the foamed layer becomes after heating and foaming. The tuned embossed sheet of the present invention is produced by forming a foamable vinyl chloride resin composition layer on the sheet base material by a method such as a calendaring method, an extrusion method, a laminating method, or a paste coating method, and then applying a gravure printing method or a flexographic method to the surface of the layer. An arbitrary design is printed by a method such as a printing method, a rotary screen printing method, or a silk screen printing method, and the surface of the foamable vinyl chloride resin composition layer printed with this arbitrary design is coated with a calendar method, an extrusion method, a laminating method, After forming a transparent or translucent vinyl chloride resin layer by a method such as a paste coating method, foaming occurs in the foamable vinyl chloride resin composition layer corresponding to the area where the printing ink layer containing the foaming accelerator is formed. The foamable vinyl chloride resin composition layer is heated and foamed at a temperature higher than the decomposition temperature of the foaming agent (preferably lower than the decomposition temperature of the foaming agent in the foaming vinyl chloride resin composition layer corresponding to the printed area that does not contain a foaming accelerator). This is obtained by forming a laminated sheet in which the printed design and the uneven design match, and then performing heat embossing (mechanical embossing) using an embossing roll provided with an arbitrary drawing pattern. This embossing method follows a process in which a foaming furnace and embossing device are installed separately, and first heats and foams in the foaming furnace (chemical embossing), then reheats and mechanically embosses (offline), and immediately after the foaming furnace. There are two methods of heating and mechanical embossing immediately after foaming (chemical embossing) using a device equipped with an embossing device (in-line), but either method is applicable. When embossing is performed offline, the formed foamable vinyl chloride resin composition layer is completely cooled, so the foam cells are not destroyed by the pressure of the embossing roll, and the surface roughness of the sheet surface is prevented. However, it is possible to apply heating conditions that do not cause the undecomposed foaming agent remaining in the foamable vinyl chloride resin composition layer to decompose, resulting in secondary foaming and destruction of the foam cells. On the other hand, when performing mechanical embossing immediately after heating and foaming in-line, the foamable vinyl chloride resin composition layer is in a softened state, so the back side of the sheet is cooled as much as possible, and the front surface is coated with the foamable vinyl chloride resin composition layer. It is necessary to perform mechanical embossing by heating under conditions that do not cause secondary foaming of the undecomposed foaming agent remaining in the resin composition layer. Further, during mechanical embossing, performing so-called clearance embossing in which a gap is provided between the embossing roll and the rubber roll (backup roll) is effective in preventing foam cell destruction of the foam layer. The clear lath (gap) in this case varies somewhat depending on the foaming ratio of the foam layer and the average degree of polymerization of the vinyl chloride resin forming the foam layer, so it is necessary to set it after checking each. For example, when the foaming ratio of the foam layer is 2.5 times or less, the average degree of polymerization of the thermoplastic synthetic resin forming the foam layer is 1200 or more, and the foam layer is heated under heating conditions that do not cause secondary foaming, the embossing roll is heated. By performing mechanical embossing at a pressure of 2 to 3 kg/cm 2 (gauge pressure), it is possible to easily obtain the desired synchronized embossed sheet without destruction of foam cells, even without providing the above-mentioned clearance. When the foaming ratio of the foam layer exceeds 2.5 times, it is preferable to provide a clearance as the foaming ratio increases. Furthermore, the heater for heating the sheet used during this mechanical embossing process is preferably, for example, an electric heater, an infrared or far-infrared heater, a ceramic heater, or the like. In addition, this embossing roll has a design formed by mill pressing, etching, electroforming, and heat-resistant materials such as silicone resin to form any drawing pattern on the sheet surface. Any type of material can be used, such as synthetic resin with a design formed on the surface of the sheet to form an arbitrary drawing pattern, but electroforming is particularly useful because it can express the surface shape as it is from natural materials. An embossing roll made of a synthetic resin such as silicone is preferred, and an electroforming embossing roll is preferred from the viewpoints of durability, shape retention (little dimensional change or shape change due to temperature change), and ability to be cooled. [Function] In the present invention, a foamable vinyl chloride resin composition layer is formed on the surface of a sheet base material, an arbitrary pattern is printed on the surface with a printing ink containing a foaming accelerator, and a transparent or Translucent vinyl chloride resin layers are laminated to form a laminated sheet, and then this laminated sheet is heated to foam the foamable vinyl chloride resin composition layer to create an uneven pattern. Using an embossing roll with a design of an arbitrary shape engraved on the roll periphery, mechanical embossing is performed to form a drawn design on the surface of the sheet raised by the foaming, using a heated embossing method to create a printed design and an uneven design. It is possible to easily and economically produce a harmonized embossed sheet rich in design, in which the embossed sheets coincide with each other and have a delicate and sharp drawing design formed on its surface. In addition, the average degree of polymerization of the vinyl chloride resin used in the foamable vinyl chloride resin composition layer is 1200 or more, and the average degree of polymerization of the synthetic resin used in the transparent or translucent vinyl chloride resin layer is: The average polymerization degree of the foamable vinyl chloride resin composition layer is 100 or more higher than that of the foamable vinyl chloride resin composition layer, and the foaming ratio of the foamable vinyl chloride resin composition layer is 4 times or less, so that an embossing roll is used. During embossing, the foamable vinyl chloride resin composition layer, which is heated and softened or melted, is pressed by the embossing roll, causing no problems such as foam cell destruction or roughening of the surface of the sheet. Synchronized embossed sheets can be easily produced. Furthermore, by making the printing ink layer a multi-colored printing ink layer, the present invention can obtain a complex and delicate sheet with excellent decorative properties. It is suitable for use in sheets, shoes, bags, furniture, etc. [Examples] Examples of the present invention will be described in detail below. Examples 1 to 2, Comparative Example 1 The method for manufacturing the synchronized embossed sheet of this example is as follows:
First, using a test coater with an effective mechanical width of 450 mm, a 0.95 mm thick inorganic filler paper containing glass fiber, pulp, inorganic filler, and binder as main components was coated with a blowing agent listed in Table 1. Apply vinyl chloride resin paste () to () with a doctor knife to a thickness of 0.45 mm each, and pass this through a heating furnace set at 170°C at a speed of 2 m/min to remove the vinyl chloride resin paste. ()～
() was heated to gel. This surface is printed with a printing ink containing 10% by weight of zinc octylate, which is a foaming accelerator, leaving the joints of the wooden boards, and then the wood grains and joints are printed on the surface using regular ink. After that, the transparent vinyl chloride resin paste () listed in Table 1 was applied with a doctor knife to a thickness of 0.3 mm, and passed through a heating furnace set at 170°C at a speed of 2 m/min. gelatinized vinyl chloride resin paste (). After that, heat the heating furnace set at 190℃ to 1.0~1.4℃.
The total thickness immediately after foaming is 2.0 m/min.
~2.2mm, and an embossing device installed in-line immediately after heating produces a foamable vinyl chloride resin composition using an electroforming embossing roll with a built-in electric heater that gives the grain design of natural wood. Embossing was performed by heating the layer to a temperature that would not cause secondary foaming (the clearance between the embossing roll and the back-up roll was set to 1.8 mm, and the pressing force of the embossing roll was 2 Kg/cm 2 G). The results are shown in Table 2. As is clear from Table 2, when the average degree of polymerization of the vinyl chloride resin used in the foamable vinyl chloride resin paste composition is 1210 or 1455, processing can be performed without problems by setting appropriate embossing conditions. The resulting tone-embossed sheet had a delicate interlocking design similar to natural wood, and was suitable as a flooring material.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
【表】
実施例３〜４、比較例２〜３
本実施例の同調エンボスシートの製造方法は、
まず有効機械幅450mmのテストコーターを使用し、
ガラス繊維、パルプ、無機質填料およびバインダ
ーを主成分とする0.68mmの厚みの無機填料紙の表
面に、第３表に記載する発泡剤を含む塩化ビニル
樹脂ペースト(D)〜(E)をドクターナイフで各々0.63
mmの厚みになるように塗布し、そののち、これを
165℃に設定した加熱炉へ２ｍ／分の速度で通過
させて、発泡性塩化ビニル樹脂ペースト(D)〜(E)を
加熱ゲル化した。
このゲル化した発泡性塩化ビニル樹脂ペースト
(D)〜(E)の表面に、実施例１と同様の木目模様の多
色グラビア印刷を施し、そののち、この印刷面上
に第３表に記載した透明性塩化ビニル樹脂ペース
ト(A)〜(C)を、第４表の組み合わせで0.18mmの厚み
になるよう塗布し、そののち、これを165℃に設
定した加熱炉に２ｍ／分の速度で通過させて、こ
の透明性塩化ビニル樹脂ペースト(A)〜(C)を加熱ゲ
ル化して積層シートを形成した。
次に、この積層シートを195℃に設定した加熱
炉内に1.0〜1.4ｍ／分の速度で通過させ、発泡性
塩化ビニル樹脂ペースト(D)〜(E)を発泡させ、この
発泡直後の総厚を1.9〜2.1mmとし、加熱炉の直後
にインラインで設置されているエンボス装置で、
天然木そのままの木目意匠を付した電鋳方式によ
るエンボスロールを使用して、ヒータ加熱により
加熱エンボス加工を行つた（電気ヒータ：発泡性
塩化ビニル樹脂組成物層が２次発泡しない程度の
加熱条件、エンボスロールとバツクアツプロール
とのクリアランス：０mm、エンボスロールの押
圧：２Kg／cm2Ｇ）。
その結果を第４表に示す。[Table] Examples 3-4, Comparative Examples 2-3 The method for manufacturing the synchronized embossed sheet of this example is as follows:
First, we used a test coater with an effective machine width of 450 mm.
Apply vinyl chloride resin pastes (D) to (E) containing the blowing agents listed in Table 3 onto the surface of 0.68 mm thick inorganic filler paper containing glass fiber, pulp, inorganic filler, and binder as main components using a doctor knife. and 0.63 each
Apply to a thickness of mm, then apply this
The expandable vinyl chloride resin pastes (D) to (E) were heated and gelled by passing through a heating furnace set at 165° C. at a speed of 2 m/min. This gelled foamable PVC resin paste
Multicolor gravure printing with the same wood grain pattern as in Example 1 was applied to the surfaces of (D) to (E), and then the transparent vinyl chloride resin paste (A) listed in Table 3 was applied on this printed surface. ~(C) was coated to a thickness of 0.18 mm using the combinations shown in Table 4, and then passed through a heating furnace set at 165°C at a speed of 2 m/min to form this transparent vinyl chloride. The resin pastes (A) to (C) were heated to gel to form a laminated sheet. Next, this laminated sheet is passed through a heating furnace set at 195°C at a speed of 1.0 to 1.4 m/min to foam the foamable vinyl chloride resin pastes (D) to (E). The embossing device has a thickness of 1.9 to 2.1 mm and is installed in-line immediately after the heating furnace.
Using an electroforming embossing roll with a grain design similar to that of natural wood, heat embossing was performed by heating with a heater (electric heater: heating conditions such that the foamable vinyl chloride resin composition layer did not undergo secondary foaming). , clearance between embossing roll and back-up roll: 0 mm, pressure of embossing roll: 2 Kg/cm 2 G). The results are shown in Table 4.
【表】【table】
【表】【table】
【表】【table】
本発明によれば、シートの印刷意匠とケミカル
エンボス加工によるシートの凹凸意匠とを一致さ
せ、かつこのケミカルエンボス加工により隆起し
たシート表面に繊細でシヤープな絞意匠の現出を
可能にした同調エンボスシートを提供することが
できる。
According to the present invention, the synchronized embossing makes it possible to match the printed design of the sheet with the uneven design of the sheet created by chemical embossing, and to create a delicate and sharp drawn design on the surface of the sheet raised by the chemical embossing. sheets can be provided.
Claims (1)
性塩化ビニル系樹脂組成物層と、発泡促進剤を含
む印刷インクよりなる柄模様状の印刷インク層
と、透明もしくは半透明の塩化ビニル系樹脂層と
を積層して積層シートを形成し、そののち該積層
シートを加熱して前記発泡性塩化ビニル系樹脂組
成物層を発泡させて凹凸模様を現出せしめ、次い
でその表面に任意の形状の意匠をロール周面に刻
設したエンボスロールにより絞模様を形成し、印
刷模様と凹凸模様とが一致した同調エンボスシー
トを製造する方法において、前記発泡性塩化ビニ
ル系樹脂組成物層に使用される塩化ビニル系樹脂
の平均重合度を1200以上、かつ透明もしくは半透
明の塩化ビニル系樹脂層に使用される塩化ビニル
系樹脂の平均重合度を前記発泡性塩化ビニル系樹
脂組成物層の平均重合度より100以上高いものと
なし、しかも発泡性塩化ビニル系樹脂組成物層の
発泡倍率を４倍以下としたことを特徴とする同調
エンボスシートの製造方法。1. A layer of a foamable vinyl chloride resin composition containing a foaming agent, a patterned printing ink layer made of a printing ink containing a foaming accelerator, and a transparent or translucent vinyl chloride resin composition layer on a sheet base material in this order. The resin layer is laminated to form a laminated sheet, and then the laminated sheet is heated to foam the foamable vinyl chloride resin composition layer to form an uneven pattern, and then an arbitrary shape is formed on the surface of the laminated sheet. In the method of manufacturing a synchronized embossed sheet in which a pattern is formed by an embossing roll with a design engraved on the circumferential surface of the roll, and the printed pattern and the uneven pattern match, the foamable vinyl chloride resin composition layer is The average polymerization degree of the vinyl chloride resin used in the transparent or translucent vinyl chloride resin layer is 1200 or more, and the average polymerization degree of the vinyl chloride resin used in the transparent or translucent vinyl chloride resin layer is the average polymerization degree of the foamable vinyl chloride resin composition layer. 1. A method for producing a synchronized embossed sheet, characterized in that the foaming ratio of the foamable vinyl chloride resin composition layer is 4 times or less.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61243218A JPS6397639A (en) | 1986-10-15 | 1986-10-15 | Production of synchronous embossed sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61243218A JPS6397639A (en) | 1986-10-15 | 1986-10-15 | Production of synchronous embossed sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6397639A JPS6397639A (en) | 1988-04-28 |
| JPH0431498B2 true JPH0431498B2 (en) | 1992-05-26 |
Family
ID=17100582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61243218A Granted JPS6397639A (en) | 1986-10-15 | 1986-10-15 | Production of synchronous embossed sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6397639A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6397639A (en) * | 1986-10-15 | 1988-04-28 | Achilles Corp | Production of synchronous embossed sheet |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3196062A (en) * | 1961-09-27 | 1965-07-20 | Du Pont | Production of embossed plastic sheet material |
| US3458337A (en) * | 1966-06-06 | 1969-07-29 | Gaf Corp | Method for making covering materials incorporating foamed resin material and product thereof |
| US3844814A (en) * | 1966-07-06 | 1974-10-29 | Gen Aniline & Film Corp | Foamed decorative covering material and method of manufacture |
| JPS53104680A (en) * | 1976-12-27 | 1978-09-12 | Dowdflor Corp | Cushioning sheet product and its production method |
| US4409280A (en) * | 1981-09-21 | 1983-10-11 | Mannington Mills | Decorative surface coverings |
| JPS6397639A (en) * | 1986-10-15 | 1988-04-28 | Achilles Corp | Production of synchronous embossed sheet |
-
1986
- 1986-10-15 JP JP61243218A patent/JPS6397639A/en active Granted
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3196062A (en) * | 1961-09-27 | 1965-07-20 | Du Pont | Production of embossed plastic sheet material |
| US3458337A (en) * | 1966-06-06 | 1969-07-29 | Gaf Corp | Method for making covering materials incorporating foamed resin material and product thereof |
| US3844814A (en) * | 1966-07-06 | 1974-10-29 | Gen Aniline & Film Corp | Foamed decorative covering material and method of manufacture |
| JPS53104680A (en) * | 1976-12-27 | 1978-09-12 | Dowdflor Corp | Cushioning sheet product and its production method |
| US4409280A (en) * | 1981-09-21 | 1983-10-11 | Mannington Mills | Decorative surface coverings |
| JPS6397639A (en) * | 1986-10-15 | 1988-04-28 | Achilles Corp | Production of synchronous embossed sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6397639A (en) | 1988-04-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |