JPH0376663B2 - - Google Patents
Info
- Publication number
- JPH0376663B2 JPH0376663B2 JP9736284A JP9736284A JPH0376663B2 JP H0376663 B2 JPH0376663 B2 JP H0376663B2 JP 9736284 A JP9736284 A JP 9736284A JP 9736284 A JP9736284 A JP 9736284A JP H0376663 B2 JPH0376663 B2 JP H0376663B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- mol
- evoh
- polyvinyl chloride
- vinyl acetate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000009823 thermal lamination Methods 0.000 claims description 27
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 25
- 239000005977 Ethylene Substances 0.000 claims description 25
- 239000010410 layer Substances 0.000 claims description 24
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 12
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 10
- 238000007127 saponification reaction Methods 0.000 claims description 10
- 229920012485 Plasticized Polyvinyl chloride Polymers 0.000 claims description 8
- 239000012790 adhesive layer Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 5
- 229920002635 polyurethane Polymers 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 61
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 61
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 61
- 230000001070 adhesive effect Effects 0.000 description 40
- 239000004014 plasticizer Substances 0.000 description 40
- 229920000915 polyvinyl chloride Polymers 0.000 description 39
- 239000004800 polyvinyl chloride Substances 0.000 description 39
- 239000000853 adhesive Substances 0.000 description 38
- 230000000903 blocking effect Effects 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical group CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 230000005012 migration Effects 0.000 description 12
- 238000013508 migration Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000008859 change Effects 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 4
- -1 acrylic ester Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 229940032007 methylethyl ketone Drugs 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 229920006243 acrylic copolymer Polymers 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000004049 embossing Methods 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 239000004840 adhesive resin Substances 0.000 description 2
- 229920006223 adhesive resin Polymers 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007795 chemical reaction product 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
- 239000000428 dust Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 2
- JQCXWCOOWVGKMT-UHFFFAOYSA-N phthalic acid diheptyl ester Natural products CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- BAZVBVCLLGYUFS-UHFFFAOYSA-N 1-o-butyl 2-o-dodecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC BAZVBVCLLGYUFS-UHFFFAOYSA-N 0.000 description 1
- 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
- WGQVJOPQTOUKDI-UHFFFAOYSA-N 2-dodecoxycarbonylbenzoic acid Chemical compound CCCCCCCCCCCCOC(=O)C1=CC=CC=C1C(O)=O WGQVJOPQTOUKDI-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- PGIBJVOPLXHHGS-UHFFFAOYSA-N Di-n-decyl phthalate Chemical compound CCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCC PGIBJVOPLXHHGS-UHFFFAOYSA-N 0.000 description 1
- VOWAEIGWURALJQ-UHFFFAOYSA-N Dicyclohexyl phthalate Chemical compound C=1C=CC=C(C(=O)OC2CCCCC2)C=1C(=O)OC1CCCCC1 VOWAEIGWURALJQ-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
- IJFPVINAQGWBRJ-UHFFFAOYSA-N Diisooctyl phthalate Chemical compound CC(C)CCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCC(C)C IJFPVINAQGWBRJ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 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
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000008901 benefit 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
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- DROMNWUQASBTFM-UHFFFAOYSA-N dinonyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCC DROMNWUQASBTFM-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 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
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000004702 methyl esters Chemical class 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
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010345 tape casting Methods 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
- 238000002834 transmittance Methods 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 229940093635 tributyl phosphate Drugs 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Description
ãçºæã®è©³çŽ°ãªèª¬æã
 æ¬çºæã®æè¡åé
æ¬çºæã¯è¡šé¢ã®çæ¹ããç¹å®ã®ïŒçš®ã®æ¥çå€ã®
ç¹å®ã®æ··åæ¯ãããªãæš¹èå±€ã§è¢«èŠãããŠãªãè
ããããã³ã°æ§ã«åªããŸãã¹ãªããæ§ã«ãããŠã
åé¡ããªãã奜é©ã«å®çšã«äŸãåŸãç±ã©ãããŒã·
ãšã³çšã®ç¹å®çµæã®ãšãã¬ã³âé
¢é
žããã«å
±éå
äœããåç©ãã€ã«ã ã«é¢ãããDETAILED DESCRIPTION OF THE INVENTION A Technical Field of the Invention The present invention provides a material having excellent blocking resistance and slip resistance, in which one of the surfaces is coated with a resin layer consisting of a specific mixing ratio of two specific types of adhesives. The present invention relates to a saponified ethylene-vinyl acetate copolymer film having a specific composition for thermal lamination that can be used practically without any problems.
 åŸæ¥æè¡ããã³ãã®åé¡ç¹
åŸæ¥ããçšããããŠããäžè¬ã«è»è³ªããªå¡©åã
ãã«ãšç§°ããããŠããå¯å¡åããªå¡©åããã«ã®ã
ã€ã«ã ãŸãã¯ã·ãŒãã¯ãå·¥æ¥çã«ã¯ãçŽ25ééïŒ
以äžãå€ãã®å Žå30ééïŒ
以äžã®å€éã®å¯å¡å€ã
é
åãããŠããã®ãéåžžã§ããããã®ããã«è©²ã·
ãŒãçã¯å¥œé©ãªç¹æ§ã掻ãããŠåºãçšããããŠã
ããã®ã®ãå¯å¡å€ãè¡šé¢ã«ç§»è¡ã滲åºãããšãã
倧ããªæ¬ ç¹ãæããŠããã該衚é¢ã被èŠãã該æ¬
ç¹ãæé€ããã被èŠæãæ±ããããŠãããB. Prior Art and its Problems Conventionally used plasticized polyvinyl chloride films or sheets, generally referred to as flexible polyvinyl chloride, have an industrial content of about 25% by weight.
As mentioned above, in most cases, a large amount of plasticizer (more than 30% by weight) is usually blended, and for this reason, although the sheet etc. is widely used to take advantage of its favorable properties, the plasticizer migrates to the surface. However, there is a need for a coating material that can cover the surface and eliminate this drawback.
è»è³ªããªå¡©åããã«ã·ãŒããããšãã°ãã¹ã¯ã
ãããæžé¡ããªããŒã«äœ¿çšãããšéé»æ°è€åæ©ã§
ã³ããŒãããæžé¡ãšæ¥ããå Žåã«ã¯ã極ããŠçæ
éã®ãã¡ã«å°å·ã€ã³ã¯ãè»è³ªããªå¡©åãããŒã«ã·
ãŒãã«ä»çããŠããŸããæžé¡ãç Žæããããè»è³ª
å¡©åããã«ã·ãŒããæ±æãã該ã·ãŒããéããŠã
å°å·é¢ã®æåçãèªã¿ãšãããšãã§ããªããªããš
ããåé¡ãããããŸãè»è³ªããªå¡©åããã«ãããª
ããæè¬ãå¡©ãã¬ã¶ãŒãææãšããŠã€ããããã
è¥ããã¯è©²ã¬ã¶ãŒã§è¢«èŠãããŠãªã家å
·é¡ãäºå
çšä»åšçãããã«ã¯å®è³ªçã«è»è³ªããªå¡©åããã«
ãããªãå£çŽçã«ãããŠãå¯å¡å€ã®è¡šé¢ãžã®ç§»
è¡ã滲åºã«èµ·å ããŠæ±æãæãããã€è©²æ±æãæ
ããšãé£ããšãã解決ãããã°ãªããªã課é¡ãã
ããããã«è»è³ªããªå¡©åããã«ã®ãã€ã«ã ãŸãã¯
ã·ãŒãã¯èŸ²æ¥çšãšããŠããŠã¹æ œå¹çã«ãããŠããª
ãªã¬ãã€ã³ã®ãã€ã«ã ãŸãã¯ã·ãŒãã«æ¯ããä¿æž©
æ§ã«åªãããªã©ã®é·æã掻ããã奜é©ã«äœ¿çšãã
ãŠããããæ¯èŒçé·æã«äºãã䜿çšãããšãå¯å¡
å€ãè¡šé¢ã«ç§»è¡ã»æ»²åºããŠæ±ããããã«å
ç·éé
çãäœäžãããšããæ¬ ç¹ããããããã«ãåæ§ã®
æè¡èª²é¡ããããè©²æ¬ ç¹ãæ¹åãããšããè©Šã¿
ã¯ã幟å€ã¿ããããã該ç®çãéæããæºè¶³ã«å®
çšã«äŸãããããã®ã¯æªã èŠåºãããŠããããå¯
å¡å€è¡šé¢æ»²åºã®ãªãè»è³ªããªå¡©åããã«ç³»ãã€ã«
ã ãŸãã¯ã·ãŒããåŸ
æãããŠããã®ãå®æ
ã§ã
ãã If a soft PVC sheet is used for a desk mat or document holder, for example, and it comes into contact with a document copied by an electrostatic copier, the printing ink will adhere to the soft PVC sheet in a very short period of time, causing the document to become damaged. If the soft vinyl chloride sheet is damaged or the soft vinyl chloride sheet becomes contaminated,
There is a problem in that characters on the printed surface cannot be read. In addition, it is made from soft polyvinyl chloride, so-called PVC leather.
Furniture, office equipment, etc. coated with the leather, and even wallpaper made essentially of soft polyvinyl chloride, are susceptible to contamination due to migration and exudation of the plasticizer onto the surface. There is a problem that must be solved that the contamination is difficult to wipe off. Furthermore, soft polyvinyl chloride films or sheets are preferably used for agricultural purposes such as greenhouse cultivation due to their superior heat retention properties compared to polyolefin films or sheets, but over a relatively long period of time, When used, the plasticizer migrates to the surface and oozes out, staining the surface, resulting in a decrease in light transmittance, which poses a similar technical problem. Although there have been many attempts to improve this drawback, no one has yet been found that achieves the objective and is satisfactorily put to practical use. The reality is that seats have been long-awaited.
ä»æ¹è©²è»è³ªããªå¡©åããã«ãããªããã€ã«ã ãŸ
ãã¯ã·ãŒãã«ä»ã®ç±å¯å¡æ§ãã€ã«ã ãç©å±€ããŠè©²
æ¬ ç¹ãæé€ããããšããè©Šã¿ãããã該被èŠãã€
ã«ã ãšããŠå®çšãããŠãããã®ã«ã¯ãæ¥çå€ãçš
ããã«å®è³ªäžè»è³ªããªå¡©åããã«ãããªããã€ã«
ã ãŸãã¯ã·ãŒãã«ç±ã©ãããŒã·ãšã³æ³ã§å®¹æã«æ¥
çãã被èŠå±€ã圢æãããã¢ã¯ãªã«ç³»æš¹èãã€ã«
ã ããããããã該å¯å¡å€ç§»è¡æ»²åºé²æ¢å¹æã¯å®
質çã«æ®ãã©èŠãããªããä»ã®ç±å¯å¡æ§æš¹èã¯ã
æ¥çå€ã®äœ¿çšãªãã§ã¯æã容æã§ããã該ããªå¡©
åããã«ç³»ãã€ã«ã ãŸãã¯ã·ãŒã補é æ¥è
ã«å®¹æ
ã«åãå
¥ããããæè¡çã«æãåçŽåãã容æã«
æ¡çšããåŸãç±ã©ãããŒã·ãšã³æ³ã§è»è³ªããªå¡©å
ããã«ãã€ã«ã åã¯ã·ãŒãã«æ¥çããã該被èŠã
æœããããšã¯ã§ããªãããããäºæ
ããåèšã¢ã¯
ãªã«ç³»æš¹èãšåæ§ã«æ¥çå€ã®å¡åžæäœãåèšè£œé
æ¥è
ãè¡ãããšãªããçŽã¡ã«ç±ã©ãããŒã·ãšã³æ³
ã«ããè¯å¥œãªæ¥çåããã€ãŠè©²è¢«èŠãæœããããš
ãã§ãããããåèšå¯å¡å€ã®è¡šé¢ãžã®ç§»è¡ã»æ»²åº
ã䜵ããŠé²æ¢ãåŸãç±ã©ãããŒã·ãšã³çšãã€ã«ã
ã匷ãæ±ããããŠããã On the other hand, there have been attempts to eliminate this drawback by laminating other thermoplastic films on the flexible polyvinyl chloride film or sheet. Examples of coating films that have been put into practical use include acrylic resin films that can be easily adhered to a film or sheet substantially made of soft polyvinyl chloride by thermal lamination without using an adhesive to form a coating layer. There is. However, the effect of preventing the plasticizer migration and oozing is practically not observed. Other thermoplastic resins are
The flexible polyvinyl chloride film or sheet can be fabricated without the use of adhesives by the thermal lamination method, which is the easiest and most easily accepted by the polyvinyl chloride film or sheet manufacturers, and which is technologically the most simple and easily adopted. It is glued to the sheet and the coating cannot be applied. Under these circumstances, as with the acrylic resin, the manufacturer can immediately apply the coating with good adhesive strength by thermal lamination without having to apply an adhesive. There is a strong need for a film for thermal lamination that can also prevent the migration and oozing of the liquid onto the surface.
 æ¬çºæã®æ§æãç®çããã³äœçšå¹æ
æ¬çºæã¯ãè¡šé¢ã®çæ¹ããå¡©åããã«æåã60
ã99ã¢ã«ïŒ
ããã³é
¢é
žããã«ããã³ïŒãŸãã¯ïŒã¡
ã¿ïŒã¢ã¯ãªã«é
žãšã¹ãã«æåã40ãïŒã¢ã«ïŒ
å«ã
å¡©åããã«å
±éåäœ(A)ãšã€ãœã·ã¢ããŒãåºãå«ã
åå¿åããªãŠã¬ã¿ã³ç³»é«åå(B)ãããªãã該混å
å²åïŒééïŒãïŒïŒ¢ïŒ2/3ãïŒã§ããæ¥çå€å±€
ã§è¢«èŠããããšãã¬ã³å«é20ã60ã¢ã«ïŒ
ãé
¢é
žã
ãã«æåã®ããå床95ïŒ
以äžã®ãšãã¬ã³âé
¢é
žã
ãã«å
±éåäœããåç©ïŒä»¥äžEVOHãšèšããïŒã
ããªãç±ã©ãããŒã·ãšã³çšãã€ã«ã ãæäŸãããš
ãããã®ã§ãããC Structure, purpose, and effect of the present invention The present invention is characterized in that one of the surfaces contains 60% vinyl chloride component.
Consisting of a vinyl chloride copolymer (A) containing ~99 mol% and 40 to 1 mol% of vinyl acetate and/or (meth)acrylic acid ester components, and a reactive polyurethane polymer (B) containing an isocyanate group, An ethylene-vinyl acetate copolymer with an ethylene content of 20 to 60 mol% and a saponification degree of vinyl acetate component of 95% or more, coated with an adhesive layer with a mixing ratio (weight) of A/B = 2/3 to 6. The present invention aims to provide a film for thermal lamination made of EVOH (hereinafter referred to as EVOH).
æ¬çºæã®ç±ã©ãããŒã·ãšã³çšãã€ã«ã ã¯èãã
ããã³ã°æ§ããã³ã¹ãªããæ§ã«åªããããã«åçš®
ç±å¯å¡æ§æš¹èãã€ã«ã ãŸãã¯ã·ãŒããããã¯çŽãª
ã©ã«å¯Ÿãåªããæ¥çæ§ã瀺ãããŸãã©ãããŒã·ãš
ã³ãããŸã§ã®çµæå£åãå°ãªããããã«ã©ãããŒ
ã·ãšã³åŸã®æ¥çæ§ã®å£åãªã©ãå°ãªãããŸãèå¯
å¡å€æ§ãèå¯å¡å€ç§»è¡ã»æ»²åºæ§ãåªããŠããã
ããèæ±ææ§ã«åªããããã«æž
ææ§ãè¯å¥œã§ã
ãã The film for thermal lamination of the present invention has excellent blocking resistance and slip property, and also exhibits excellent adhesion to various thermoplastic resin films, sheets, and papers, and has little deterioration over time before lamination. There is also little deterioration in adhesive properties after lamination. Furthermore, it has excellent plasticizer resistance and plasticizer migration/exudation resistance, so it has excellent stain resistance and also has good wiping properties.
ãšãã«æ¬çºæã®ç±ã©ãããŒã·ãšã³çšãã€ã«ã ã¯
å¯å¡å€ãå«æããããªå¡©åããã«ãã€ã«ã ãŸãã¯
ã·ãŒãã«ç©å±€ãããšãã«èå¹ã瀺ãã In particular, the thermal lamination film of the present invention exhibits remarkable effects when laminated on a polyvinyl chloride film or sheet containing a plasticizer.
 æ¬çºæã®ãã詳现ãªèª¬æ
æ¬çºæã®ç±ã©ãããŒã·ãšã³çšãã€ã«ã ãšããã
ãã«æãéèŠãªèŠä»¶ã®äžã€ã¯EVOHãã€ã«ã ã®
è¡šé¢ã®çæ¹ã被èŠããç±æ¥çæ§ãæããæš¹èã«ã
ãã該暹èã¯ãEVOHã«è¯å¥œãªæ¥çæ§ã瀺ããš
ãšãã«ç±ã©ãããŒãããçŽ æãããšãã°å¯å¡åã
ãªå¡©åããã«ãšãæ¥çæ§ãè¯å¥œã§ãªããã°ãªã
ããããã«è©²è¢«èŠãæœããããEVOHãã€ã«ã
ãèããããã³ã°æ§ãæããã¹ãªããæ§ã«ãããŠ
ãè¯å¥œã§ããããããç±ã©ãããŒã·ãšã³çšãã€ã«
ã ãšããŠã該被èŠãæœãããåŸã®é·æã®ã·ãšã«ã
ã©ã€ãïŒshelf lifeãç±ã©ãããŒã·ãšã³çšãã€ã«
ã ãšããŠæ§èœäœäžã®ãªãåžžæž©æŸçœ®èš±å®¹æéãã
ããïŒãæãããã®ã§ãªããã°ãªããªããæ¬çºæ
ã«çšãããã該æ¥çæ§ãæããæš¹èã¯ãå¡©åãã
ã«æåã60ã99ã¢ã«ïŒ
ããã³é
¢é
žããã«æåãã
ã³ïŒãŸãã¯ïŒã¡ã¿ïŒã¢ã¯ãªã«é
žãšã¹ãã«æåã40
ãïŒã¢ã«ïŒ
å«ãå¡©åããã«ç³»å
±éåäœ(A)ãšã€ãœã·
ã¢ããŒãåºãå«ãåå¿åããªãŠã¬ã¿ã³ç³»é«åå(B)
ãšããæãããã€ïŒ¡ïŒïŒ¢ã®æ··åå²åïŒééïŒã2/
ïŒãïŒã§ããæš¹èã§ãããD. More detailed description of the present invention One of the most important requirements for the thermal lamination film of the present invention is a resin having thermal adhesive properties that coats one of the surfaces of the EVOH film. The resin must exhibit good adhesion to EVOH and also to the material to be heat laminated, such as plasticized polyvinyl chloride, and the coated EVOH film must have anti-blocking properties. It has good slip properties and has a long shelf life after being coated as a film for thermal lamination. ). The adhesive resin used in the present invention contains 60 to 99 mol% of vinyl chloride component and 40% of vinyl acetate component and/or (meth)acrylic acid ester component.
Vinyl chloride copolymer (A) containing ~1 mol% and reactive polyurethane polymer containing isocyanate groups (B)
and the mixing ratio (weight) of A/B is 2/
3 to 6.
ããã§å¡©åããã«ç³»å
±éåäœãšããŠã¯å¡©åãã
ã«æåã70ã95ã¢ã«ïŒ
ããã³é
¢é
žããã«ããã³ïŒ
ãŸãã¯ïŒã¡ã¿ïŒã¢ã¯ãªã«é
žãšã¹ãã«æåã30ãïŒ
ã¢ã«ïŒ
å«ããã®ããã奜é©ã§ããããŸãé
¢é
žãã
ã«ããã³ïŒãŸãã¯ïŒã¡ã¿ïŒã¢ã¯ãªã«é
žãšã¹ãã«æ
åãšããŠã¯é
¢é
žããã«æåãïŒã¡ã¿ïŒã¢ã¯ãªã«é
ž
ãšã¹ãã«ïŒã¡ãã«ãšã¹ãã«ããšãã«ãšã¹ãã«ãª
ã©ïŒæåãããã¯ãããã®äž¡æåãå«ããã®ãã
ããããã®ãã¡é
¢é
žããã«æåãããã¯äž¡æåã
å«ããã®ã奜é©ã§ããããããã®æåãå«ãå¡©å
ããã«ç³»å
±éåäœããã¬ã€ã³é
žãã€ã¿ã³ã³é
žãªã©
ã®äžé£œåææ©é
žãããã¯ãã®ç¡æ°Žç©ãïŒã¡ã¿ïŒã¢
ã¯ãªã«é
žãªã©ã®ç¬¬ïŒæåã«ããå€æ§ãããã®ã䜿
çšããããšãã§ããããã®ãã¡ç¡æ°Žãã¬ã€ã³é
žã«
ããå€æ§ãããã®ããã奜é©ã§ããããããã®ç¬¬
ïŒæåã®å¥œé©ãªå«æéã¯0.1ãïŒã¢ã«ïŒ
ã§ããã Here, the vinyl chloride copolymer contains 70 to 95 mol% of vinyl chloride component and vinyl acetate and/or
or (meth)acrylic acid ester component from 30 to 5
It is more preferable to use mol%. In addition, vinyl acetate and/or (meth)acrylic ester components include vinyl acetate components, (meth)acrylic ester (methyl esters, ethyl esters, etc.) components, or both of these components. It is preferable to use one or both components. It is also possible to use vinyl chloride copolymers containing these components modified with a third component such as unsaturated organic acids such as maleic acid and itaconic acid or their anhydrides, and (meth)acrylic acid. Among these, those modified with maleic anhydride are more preferred. The preferred content of these third components is 0.1 to 5 mol%.
該å
±éåäœã®æº¶å€ãšããŠã¯ã¡ãã«ãšãã«ã±ãã³
é
¢é
žãšãã«ãé
¢é
žããã«ã奜ãŸãããåžéå€ãšã
ãŠã¯ãã¡ãã«ãšãã«ã±ãã³ããã«ãšã³ãªã©ã奜é©
ã«çšãããããã€ãœã·ã¢ããŒãåºãå«ãåå¿åã
ãªãŠã¬ã¿ã³ç³»é«ååã¯ååäžã«ïŒå以äžã®æ°Žé
žåº
ãæããé«ååãããšãã°ãšãã¬ã³ã°ãªã³ãŒã«ã
ãããã¬ã³ã°ãªã³ãŒã«ãšã¢ãžãã³é
žãéçž®åããŠ
åŸãããããªãšã¹ãã«ãšãé
¢é
žããã«ãšå¡©åãã
ã«ã®å
±éåäœãéšåããåããŠåŸãããååäžã«
æ°Žé
žåºãæããé«ååãªã©ããååäžã«ïŒå以äž
ã®ã€ãœã·ã¢ããŒãåºãæããååç©ãããšãã°ïŒ
ã¢ã«ã®ïŒïŒïŒâãããµã¡ãã¬ã³ã°ãªã³ãŒã«ãšïŒã¢
ã«ã®ïŒïŒïŒâããªã¬ã³ãžã€ãœã·ã¢ããŒããšã®åå¿
ç©ãšããïŒã¢ã«ã®ããªã¡ãããŒã«ãããã³ãšïŒã¢
ã«ã®ããªã¬ã³ãžã€ãœã·ã¢ããŒããšã®åå¿ç©ãšæ··å
ããŠåŸããããã®ã§ãããããã«ååäžã«ïŒåã®
ã€ãœã·ã¢ããŒãåºãæããååç©åç¬ã§ãããã
該é«ååã®æº¶å€ãšããŠã¯ã€ãœã·ã¢ããŒãåºãšã®å
å¿æ§ããªããé
¢é
žãšãã«ãé
¢é
žããã«ãã¡ãã«ãš
ãã«ã±ãã³ããã«ãšã³ããã·ã¬ã³ãªã©ã奜é©ã«çš
ããããã The solvent for the copolymer is preferably methyl ethyl ketone, ethyl acetate, or butyl acetate, and the diluent is preferably methyl ethyl ketone, toluene, or the like. Reactive polyurethane polymers containing isocyanate groups are polymers having two or more hydroxyl groups in the molecule, such as ethylene glycol,
Polyester obtained by polycondensation of propylene glycol and adipic acid, or polymers with hydroxyl groups in the molecule obtained by partial saponification of a copolymer of vinyl acetate and vinyl chloride, etc. Compounds having groups, e.g. 1
One obtained by mixing a reaction product of 1,6-hexamethylene glycol with 2 moles of 2,4-tolylene diisocyanate, or a reaction product with 1 mole of trimethylolpropane and 3 moles of tolylene diisocyanate. It is. Furthermore, a compound having two isocyanate groups in the molecule may be used alone.
As the solvent for the polymer, ethyl acetate, butyl acetate, methyl ethyl ketone, toluene, xylene, etc., which have no reactivity with isocyanate groups, are preferably used.
å¡©åããã«ç³»å
±éåäœ(A)ãåç¬ã§äœ¿çšããå Žå
ã«ã¯ãEVOHãã€ã«ã ã«è©²è¢«èŠãèšããŠããã
ãå¯å¡åããªå¡©åããã«ã·ãŒããžç±ã©ãããŒãã
ãåŸã®è©²å
±éåäœ(A)å±€ãšEVOHå±€ãšã®å±€éæ¥ç
æ§ã¯äœãå®çšäžæºè¶³ãªãã®ãšã¯ãªãåŸãªããä»æ¹
ã€ãœã·ã¢ããŒãåºãå«ãåå¿åããªãŠã¬ã¿ã³ç³»é«
åå(B)ã®åç¬äœ¿çšã®å Žåã«ã¯æ¥çåã«ãããŠã¯å
åã§ãããã該ç±ã©ãããŒã·ãšã³çšãã€ã«ã ã¯ã
ããããã³ã°æ§ã瀺ããŸãã¹ãªããæ§ãäžè¯ã§å®
çšã«äŸãåŸããã®ãšã¯ãªããªããåã³ïŒ¢ãæ··å
䜿çšããããšã«ãã€ãŠå§ããŠãè©²æ¬ ç¹ãæé€ãã
ãããç±ã©ãããŒã·ãšã³æã®æ¥çåãå
åã§ãçµ
æäœäžãå®çšäžã¿ãããªãã·ãšã«ãã©ã€ãã®é·ã
æ¬çºæã®ç±ã©ãããŒã·ãšã³çšãã€ã«ã ãåŸãããš
ãã§ããããšïŒ¢ã®æ··åå²åïŒééïŒïŒ¡ïŒïŒ¢ã2/
ïŒãïŒã®é åã«ãªããã°äžèšæ¬ ç¹ãæé€ããèã
ãããã³ã°æ§äžŠã³ã«ã¹ãªããæ§å
±ã«è¯å¥œãªè©²ãã€
ã«ã ãåŸãããšã¯ã§ããªããïŒïŒ¢ã2/3æªæºã§
ããã°ãèããããã³ã°æ§ã«ãããŠäžå
åã§ã
ããïŒãè¶ãããšæ¥çåã«ãããŠäžæºè¶³ãªãã®ãš
ãªãããã¥ãã®å Žåã«ãããŠãã·ãšã«ãã©ã€ãã
æŠããŠçãããã®ãšãªãã®ã§å¥œãŸãããªãã When the vinyl chloride copolymer (A) is used alone, the coating is provided on an EVOH film, and this is heat laminated to a plasticized polyvinyl chloride sheet, followed by the copolymer (A) layer. The interlayer adhesion with the EVOH layer is low and cannot be practically satisfactory. On the other hand, when the reactive polyurethane polymer (B) containing isocyanate groups is used alone, the adhesive strength is sufficient, but the thermal lamination film has
It exhibits blocking properties and poor slip properties, making it unsuitable for practical use. Only by using a mixture of A and B can this disadvantage be eliminated,
Furthermore, the film for thermal lamination of the present invention has sufficient adhesive strength during thermal lamination, and has a long shelf life with no practical deterioration over time. Mixing ratio of A and B (weight) A/B is 2/
If it is not in the range of 3 to 6, it will not be possible to eliminate the above-mentioned drawbacks and obtain a film with good blocking resistance and slip resistance. If A/B is less than 2/3, the blocking resistance is insufficient, and if it exceeds 6, the adhesive strength is unsatisfactory, and in either case, the shelf life is generally short, which is preferable. do not have.
該æ¥çå€ã®è©²EVOHãã€ã«ã ãžã®å¡åžéãšã
ãŠã¯ïŒã10ïœïŒm2ãéåžžïŒãïŒïœïŒm2ã§çšããã
ããã³ãŒãã€ã³ã°æäœã«ãã該æ¥çå€ã®å¡åžã¯ã
ã°ã©ãã€ã³ãŒããããŒã«ã³ãŒãããã¯ã¿ãŒããŒã«
ã³ãŒãããã¯ã¿ãŒãã€ãã³ãŒããããŒã³ãŒããã«
ãŒãã³ãããŒã³ãŒããªã©ããèªäœå
¬ç¥ã®ä»»æã®æ
段ã§è¡ãããã The amount of the adhesive applied to the EVOH film is 1 to 10 g/m 2 , usually 2 to 5 g/m 2 . Application of the adhesive by a coating operation includes:
The coating may be carried out by any means known per se, such as gravure coating, roll coating, doctor roll coating, doctor knife coating, bar coating, curtain flow coating, etc.
該ã³ãŒãEVOHãã€ã«ã ãç±ã©ãããŒããã
ã«ã¯éåžž120ã160âã§å¥œé©ã«è¡ãããšãåºæ¥ãã
ããäœã枩床ã§ã¯æ¥çåã®çºçŸãããäžå
åãªå Ž
åãã¿ãããããé«ã枩床ã§ã¯EVOHè¡šé¢ã®ç¶
æ
ã®æªåãæãå Žåãããã®ã§å¥œãŸãããªãã Thermal lamination of the coated EVOH film can normally be carried out preferably at 120 to 160°C.
At a lower temperature, the adhesive force may not be developed sufficiently, and at a higher temperature, the condition of the EVOH surface may deteriorate, which is not preferable.
æ¬çºæã«çšããããEVOHã¯ããšãã¬ã³å«é
ã20ã60ã¢ã«ïŒ
ã奜ãŸããã¯25ã50ã¢ã«ïŒ
ã§ã
ããé
¢é
žæåã®ããå床ã95ïŒ
以äžã®ãã®ã§ã
ãã The EVOH used in the present invention has an ethylene content of 20 to 60 mol%, preferably 25 to 50 mol%, and a saponification degree of the acetic acid component of 95% or more.
次ã«æ¬çºæã®ç±ã©ãããŒã·ãšã³ãã€ã«ã ã¯å¯å¡
åããªå¡©åããã«ãã€ã«ã ãŸãã¯ã·ãŒããããªã
ã¡å¯å¡å€ãå«æããå¯å¡åããªå¡©åããã«ãã€ã«
ã ãŸãã¯ã·ãŒããšç©å±€ãããšããèå¹ã瀺ãã®
ã§ã以äžãã®ç¹ã«ã€ããŠèª¬æããã Next, since the thermal lamination film of the present invention exhibits remarkable effects when laminated with a plasticized polyvinyl chloride film or sheet, that is, a plasticized polyvinyl chloride film or sheet containing a plasticizer, this point will be explained below. .
ããã§å¯å¡åããªå¡©åããã«ãã€ã«ã ãŸãã¯ã·
ãŒããšããŠã¯æ¬¡ã«ããã20âã§æ¶²ç¶ã§ããå¯å¡å€
ãå
šééã«å¯Ÿã25ã55ééïŒ
å«æãããã®ããã
ãããã20âã§æ¶²äœã§ããå¯å¡å€ãšããŠã¯ããšã
ã°èç¹20â以äžã®ãžãŒããã«ãã¿ã¬ãŒãããžâïŒ
âãšãã«ããã·ã«ãã¿ã¬ãŒãããžâã€ãœãªã¯ãã«
ãã¿ã¬ãŒãããžâã€ãœâãã·ã«ãã¿ã¬ãŒãããžâ
ãã·ã«ãã¿ã¬ãŒãããžâããã«ãã¿ã¬ãŒãããžâ
ã©ãŠãªã«ãã¿ã¬ãŒããããã«ã©ãŠãªã«ãã¿ã¬ãŒ
ããããã«ãã³ãžã«ãã¿ã¬ãŒããªã©ã®ãã¿ã¬ãŒã
ç³»å¯å¡å€ãããªã¯ã¬ãžã«ãã¹ããšãŒããããªâã
ãã«ãã¹ããšãŒããããªâïŒâãšãã«ããã·ã«ã
ã¹ããšãŒããªã©ã®ãã¹ããšãŒãç³»ãå¡©çŽ åãã©ã
ã€ã³ãªã©ã®å«å¡©çŽ ç³»å¯å¡å€ãªã©ããããåžžæž©ã§åº
äœã§ããå¯å¡å€ããšãã°ãžâã·ã¯ãããã·ã«ãã¿
ã¬ãŒããã¢ã«ã³ãŒã«ã®ççŽ æ°ã13以äžã®ãã¿ã«é
ž
ãžãšã¹ãã«çã®ãã¿ã¬ãŒãç³»å¯å¡å€ãžãã³ã¿ãšãª
ã¹ãªããŒã«èèªé
žãšã¹ãã«çã®å€äŸ¡ã¢ã«ã³ãŒã«ç³»
å¯å¡å€ããªãªã¯ãã«ããªã¡ãªããŒããªã©ã®ããªã¡
ãªããé
žç³»å¯å¡å€ãªã©ãããããããã®ãã®ã«å¯Ÿ
ããŠãšãã¬ã³å«éã60ã¢ã«ïŒ
以äžã該ããå床ã
95ïŒ
以äžã®EVOHã¯ãèå¯å¡å€æ§ããã³èå¯å¡
å€ç§»è¡ã»æ»²åºæ§ã瀺ãã該å¯å¡å€ã®äžã§ãåè
ã¯ãç¹ã«ç§»è¡ã»æ»²åºæ§ãèããå¯å¡å€ã§ããã該
EVOHã¯ãããã®å¯å¡å€ã®æ¥µããŠèãã移è¡ã»
滲åºããé²æ¢ããããšãã§ãããå°±äžããšãã¬ã³
å«éã55ã¢ã«ïŒ
以äžãã奜ãŸããã¯50ã¢ã«ïŒ
以äž
ã®é åã®EVOHã¯ã極ããŠæºè¶³ãªè©²ç¹æ§ããã¡
å¯å¡å€ééæ§ãå®è³ªäžå
šã瀺ããªãã Here, examples of the plasticized polyvinyl chloride film or sheet include those containing 25 to 55% by weight of the following plasticizer which is liquid at 20°C based on the total weight. Examples of plasticizers that are liquid at 20°C include dibutyl phthalate and di-2, which have a melting point of 20°C or less.
-Ethylhexyl phthalate, di-isooctyl phthalate, di-iso-decyl phthalate, di-
Decyl phthalate, di-nonyl phthalate, di-
Phthalate plasticizers such as lauryl phthalate, butyl lauryl phthalate, and butylpenzyl phthalate, phosphate plasticizers such as tricresyl phosphate, tri-butyl phosphate, and tri-2-ethylhexyl phosphate, and chlorine-containing plasticizers such as chlorinated paraffin. Plasticizers that are solid at room temperature include dicyclohexyl phthalate, phthalate plasticizers such as phthalate diesters whose alcohol has 13 or more carbon atoms, polyhydric alcohol plasticizers such as dipentaerythritol fatty acid esters, Examples include trimellitic acid plasticizers such as octyl trimellitate. The ethylene content is 60 mol% or less for these, and the saponification degree is
EVOH of 95% or higher indicates plasticizer resistance and plasticizer migration/leaching resistance. Among these plasticizers, the former is a plasticizer that has particularly remarkable migration and exudation properties;
EVOH causes extremely significant migration and migration of these plasticizers.
It can also prevent oozing. In particular, EVOH with an ethylene content of 55 mol % or less, preferably 50 mol % or less, has extremely satisfactory properties and exhibits virtually no plasticizer permeability.
ãšãã¬ã³å«éã®å¢å ã«äŒŽã€ãŠèå¯å¡å€ééæ§ã
次第ã«äœäžãã60ã¢ã«ïŒ
ãè¶ããé åã«è³ããšè»
質ããªå¡©åããã«ã·ãŒããŸãã¯ãã€ã«ã ã«ç©å±€ã
ããå Žåãè¡šé¢ãžã®å¯å¡å€ã®æ»²åºãã次第ã«èªã
ãããã«è³ããèæ±ææ§ãäœäžãããä»æ¹ãšãã¬
ã³å«éã®äœäžãšãšãã«èå¯å¡å€ééæ§çã®ç¹æ§
ã¯ãããåäžãããã20ã¢ã«ïŒ
æªæºã®é åã§ã¯è
æ°Žæ§ã«ä¹ãããã®ãšãªãã蟲æ¥çšãã€ã«ã çã«ã
ããŠã¯å¿è«ã®ããšãåèšãã¹ã¯ããããæžé¡ãã«
ããŒãå£çŽçã«ãããŠããããšãã°éå·Ÿçã«ã
ããå¯å¡å€ã®æ»²åºãšã¯é¢é£ããªãåãªãå€éšèŠå
ã«ããæ±æãæž
æããã«éãã該衚é¢ã®èšæœ€ãæ¹
èµ·ãããã該衚é¢ã®æå·ãæ¥ããã®ã§å¥œé©ã§ãª
ãã該ãšãã¬ã³å«éã¯25ã¢ã«ïŒ
以äžã§ããããšã
ãã奜ãŸãããæ¬çºæã®EVOHã¯ããšãã¬ã³å«
éã20ã60ã¢ã«ïŒ
ããã奜ãŸããã¯25ã50ã¢ã«ïŒ
ã®é åã«ããã°ããã該é åã«ããç°ãªããšãã¬
ã³å«éã®ïŒçš®ãŸãã¯ãã以äžããã¬ã³ããããã®
ã§ãããããšãã¬ã³å«é20ã60ã¢ã«ïŒ
ã®é åã«ã
ããEVOHã¯å®çšçã«æºè¶³ãåŸãèæ°Žæ§ãæã
ãããä»æ¹äœ¿çšç¶æ
ã«ããã平衡氎åãä¿æãåŸ
ã芪氎æ§ããªããŒã§ãããšããäžé¢ããã€ãŠãã
ããã«éé»æ°ã®çºçãæå¶ãåŸãŠãéé»æ°ã«åºã¥
ã塵åã®ä»çããªãã該芳ç¹ããã奜é©ã§ããã
該芳ç¹ããããšãã¬ã³å«éã¯50ã¢ã«ïŒ
以äžã§ãã
ããšããã奜ãŸãããããã«èå¯å¡å€æ§ãèå¯å¡
å€ã»ç§»è¡ã»æ»²åºæ§ã«ãããåªãããã€è©²ãã€ã«ã
ã®è¡šé¢ã®èæ°Žæ§ãããåäžããåŸããããåªãã
æ
æ§ã®äžã€ãšããŠæ¬çºæã«çšããEVOHãã€ã«
ã ãããé«ããšãã¬å«éããã€EVOHå±€ãšãã
ãäœããšãã¬ã³å«éããã€EVOHå±€ãããªãè€
åæ§æãšãã奜é©ãªæ
æ§ããããããªãã¡è€å
EVOHãã€ã«ã ã®è¡šé¢ã®ãã¡ã該æ¥çå€å±€ã«é£
æ¥ããäœçœ®ã«ã¯èå¯å¡å€æ§çã«ããåªãããšãã¬
ã³å«é20ã35ã¢ã«ïŒ
ã®EVOHãããŸãå€è¡šé¢ã«
ã¯èæ°Žæ§ã«ãããåªãããšãã¬ã³40ã60ã¢ã«ïŒ
ã®
EVOHãé
ãããŠãªãæ
æ§ãäžå±€å¥œé©ã§ããã
該ïŒå±€æ§æã®EVOHãã€ã«ã ã¯åèšç°ãªã
EVOHã®ïŒæã®ãã€ã«ã ãç©å±€ãããŠçšããŠã
ããããå°±äžã該ç°ãªãïŒçš®ã®EVOHãå
±æŒåº
æäœã«ãŠïŒå±€ãã€ãçšããŠãã€å
ããŸãã¯ãã€å€
ã§æº¶èç¶æ
ã®è©²ïŒçš®ã®EVOHã®æš¹èæµãäžäœå
ãããŠåŸãè¡šè£ã§åèšç°ãªãç¹æ§ãæããè€å
EVOHãã€ã«ã ããã奜é©ã«çšããããããã®
å Žå該ïŒçš®ã®EVOHå±€ã®éã«ã¯æ¥çæ§æš¹èãå¿
èŠãšããããã®ç¹ã§ããã奜ãŸããã As the ethylene content increases, the plasticizer permeability gradually decreases, and when the content exceeds 60 mol%, the leaching of the plasticizer to the surface is gradually observed when laminated to a flexible polyvinyl chloride sheet or film. As a result, stain resistance also decreases. On the other hand, as the ethylene content decreases, properties such as plasticizer permeability improve further, but in the region of less than 20 mol%, water resistance becomes poor, and this is not only useful in agricultural films, but also in desk mats and document holders. It is also not suitable for wallpaper, etc., as it may cause swelling or damage to the surface when wiping off contamination caused by mere external factors unrelated to plasticizer leaching using a rag or the like. More preferably, the ethylene content is 25 mol% or more. The EVOH of the present invention has an ethylene content of 20 to 60 mol%, more preferably 25 to 50 mol%.
It is sufficient that the ethylene content is within this range, and it may be a blend of two or more types with different ethylene contents within this range. EVOH, which has an ethylene content in the range of 20 to 60 mol%, has practically satisfactory water resistance, but on the other hand, it is a hydrophilic polymer capable of retaining equilibrium moisture under the conditions of use, so it is susceptible to static electricity. It is possible to suppress the generation of dust, and there is no adhesion of dust due to static electricity, so it is suitable from this point of view as well.
Also from this point of view, the ethylene content is more preferably 50 mol% or less. Furthermore, the EVOH film used in the present invention has a higher plasticizer resistance, better plasticizer resistance, migration, and exudation properties, and is one of the more excellent embodiments that can further improve the water resistance of the surface of the film. A preferred embodiment is a composite structure consisting of an EVOH layer with an ethylene content and an EVOH layer with a lower ethylene content. i.e. compound
On the surface of the EVOH film, adjacent to the adhesive layer, EVOH with an ethylene content of 20 to 35 mol%, which has better plasticizer resistance, etc., is used, and on the outer surface, ethylene 40 to 60%, which has a better water resistance, is used. mole%
An embodiment in which EVOH is arranged is more preferable.
The two-layer EVOH film is different from the above.
Two films of EVOH may be laminated and used, but in particular, the two different types of EVOH may be co-extruded using a two-layer die, or the two types of EVOH may be molten inside the die or outside the die. A composite material with different characteristics on the front and back surfaces obtained by integrating the EVOH resin flows of
EVOH film is more preferably used. In this case, no adhesive resin is required between the two types of EVOH layers, which is also more preferable.
EVOHã®èå¯å¡å€æ§çã¯æ¥µããŠåªãããã®ã§
ããã®ã§ãèããšããã®å¹æãçºæ®ãããã2ÎŒ
以äžã®åŠã極ããŠèãåãé åã«è³ããšãã²ã€ã
ãçã®æå·ãèµ·ãæããªãããä»æ¹ç°åžžã®æº¶èæ
èæäœã§ã¯ãã³ããŒã«ã®ãªããã€ã«ã ãåŸãã«é
ããŠãæè¡çå°é£æ§ãå¢å ãäžåæ Œåã®å¢å ãæ¥
ãã奜ãŸãããªãããŸãå€èŠ³äžã®å¥œã¿ãå
æ²¢ã®æ
å¶ãæš¡æ§ã®åæŒãçã®å¿
èŠæ§ãããšã³ãã¹å å·¥ã«
ä»ãããå Žåãå€ãããã®å Žåã«ã¯è©²EVOHã
ã€ã«ã ã®åãã¯ãå°ããšã5Ό以äžã§ããããšã
奜ãŸããããŸãEVOHãã€ã«ã ã50ÎŒãè¶ãããš
çµæžçã«ãäžå©ã«ãªãã°ããã§ãªããããšãã°è»
質ããªå¡©åããã«ã®ã·ãŒãçã®ç¹æ§ãããšãã°ã
æè»æ§ãæããªã©ç±ã©ãããŒãããçžæçŽ æã®ç¹
æ§ã«åœ±é¿ãäžãããªã©ã®ç¹ã§å¥œãŸãããªãã40ÎŒ
以äžããã奜é©ã§ããã EVOH has extremely good plasticizer resistance, so even if it is thin, it will still be effective.
When the thickness reaches the extremely thin region shown below, damage such as scratches is likely to occur, and on the other hand, with abnormal melt deposition operations, technical difficulties increase when obtaining a pinhole-free film, resulting in rejected products. This is not desirable. In addition, embossing is often applied due to the need for appearance, suppression of gloss, embossing of patterns, etc. In this case, the thickness of the EVOH film is preferably at least 5Ό or more. . Furthermore, if the EVOH film exceeds 50Ό, it is not only economically disadvantageous, but also has the characteristics of soft polyvinyl chloride sheets, etc.
This is undesirable because it affects the properties of the material to be heat laminated, such as impairing its flexibility. 40Ό
The following are more preferred.
該EVOHãã€ã«ã ã¯æªå»¶äŒžãã€æªç±åŠçã®ç¶
æ
ã§ãã€ãŠããããã寞æ³å®å®æ§ãèæ°Žæ§çã®èŠ
å°ããç±åŠçããããã®ããã奜ãŸããã
EVOHãã€ã«ã ã¯ãä»ã®æš¹èã«æ¯ãåªãããšã³
ãã¹å å·¥æ§ãæããæ¬çºæã®ç±ã©ãããŒã·ãšã³ã
ã€ã«ã ããã©ãããŒãå å·¥ã«ä»ãããåŸããšã³ã
ã¹å å·¥ãæœãããŠå¥œé©ã«äœ¿çšãããå Žåãå€ãã
ãããå Žåã«ã¯ç¡å»¶äŒžEVOHãã€ã«ã ããã奜
é©ã§ããããŸãããèæ°Žæ§ãèŠæ±ãããå Žåã«
ã¯ãå°ããšãäžè»žå»¶äŒžããããã®ãå°±äžãäºè»žæµ®
延䌞ããããã®ãäžå±€å¥œé©ã§ããããã®å Žå延䌞
åçã¯äžè»žå»¶äŒžã«ãã€ãŠã¯1.5å以äžãäºè»žå»¶äŒž
ã«ãã€ãŠã¯é¢ç©åçïŒå以äžããã奜ãŸããã¯ïŒ
å以äžãäžå±€å¥œé©ã§ããã The EVOH film may be in an unstretched and unheat-treated state, but it is more preferably heat-treated from the viewpoint of dimensional stability, water resistance, etc.
EVOH film has superior embossability compared to other resins, and the thermal lamination film of the present invention is often suitably used after being laminated and then embossed. In such a case, an unstretched EVOH film is more suitable. Further, when higher water resistance is required, it is more preferable to use at least uniaxially stretched, especially biaxially float stretched. In this case, the stretching ratio is 1.5 times or more in the case of uniaxial stretching, and the area magnification is 3 times or more in the case of biaxial stretching, more preferably 5 times.
It is more preferable that the amount is more than double that.
æ¬çºæã®ç±ã©ãããŒã·ãšã³çšãã€ã«ã ã¯åèšã®
åŠãå¯å¡åããªå¡©åããã«ãã€ã«ã ã·ãŒããžã®ç±
ã©ãããŒã·ãšã³çšãã€ã«ã ãšããŠæã奜é©ã«çšã
ãããããçŽãããªããããšãã°å£çŽçã®åºæã«
ãæ¥çæ§ã¯è¯å¥œã§ããã®ã§ãçŽãããªãåºæãã
ãã¯è£œåãžã®è¢«èŠæãšããŠãåªããè¡šé¢ã®èæ±æ
æ§ã該æ±æã®æž
ææ§äžŠã³ã«EVOHå±€ã®åªãããš
ã³ãã¹å å·¥æ§ãä»äžãåŸãŠå¥œé©ã«çšããããšãã§
ããã As mentioned above, the thermal lamination film of the present invention is most suitably used as a thermal lamination film for plasticized polyvinyl chloride film sheets, but it also has good adhesion to substrates made of paper, such as wallpaper. Therefore, it can be suitably used as a coating material for paper substrates or products as it can provide excellent surface stain resistance, ability to wipe off the stain, and excellent embossing properties of the EVOH layer. can.
次ã«æ¬çºæãå®æœäŸãæããŠèª¬æããããæ¬çº
æã®ç¯å²ãéå®ãããã®ã§ã¯ãªãã Next, the present invention will be explained with reference to examples, but the scope of the present invention is not limited.
å®æœäŸ ïŒ
ãšãã¬ã³å«é31ã¢ã«ïŒ
ãé
¢é
žããã«æåã®ãã
å床99.2ïŒ
ã®EVOHã®åã15ÎŒã®ãã€ã«ã ïŒæªå»¶
䌞ãã€ã«ã ïŒã«ã°ã©ãã€ã³ãŒã¿ãŒã§æ¥çå€ãšããŠ
ãŠã¬ã¿ã³ç³»æ¥çå€ADâ335Aãšç¡¬åå€Catâ10
ïŒæ±æŽã¢ãŒãã³ç€Ÿè£œãæ··åæ¯17ïŒïŒãåèšïŒ¢ã«å±
ããïŒãšç¡æ°Žãã¬ã€ã³é
žïŒã¢ã«ïŒ
å€æ§å¡©åããã«
86ã¢ã«ïŒ
âé
¢é
žããã«13ã¢ã«ïŒ
å
±éåäœç³»æ¥çå€
MPRâTMïŒæ¥ä¿¡ååŠç€Ÿè£œãåèšïŒ¡ã«å±ãããïŒ
ã®æ··åå²åïŒééïŒïŒ¡ïŒïŒ¢ïŒ65ïŒ35ãããªãæ¥ç
å€ã®20ééïŒ
ã®ãã«ãšã³ïŒã¡ãã«âãšãã«ã±ãã³
ïŒééæ¯ïŒïŒïŒïŒïŒã®æº¶æ¶²ãçšããŠå¡åžéïŒïœïŒm2
ïŒåºåœ¢ååºæºïŒãšãªãããã«ã³ãŒããã枩床110
âãïŒåé也ç¥ãããåŸããã該ã³ãŒããã€ã«ã
ã®ããããã³ã°æ§ã調ã¹ãããã«è©²ã³ãŒããã€ã«
ã ãšæªã³ãŒã該EVOHãã€ã«ã ãšã50ïœïŒcm2ã®
å§åã§å¯çããã24æéæŸçœ®ããåŸã®ç²çãå®çš
äžã®é害ãšãªããã©ããã調ã¹ããç²çã¯ãªãã
ããããã³ã°æ§ã«ãããŠå
šãåé¡ã®ãªãããšãèª
ããããŸã該ã³ãŒããã€ã«ã ã®ã¹ãªããæ§ãè¯å¥œ
ã§ãã€ãã該åŸãããã³ãŒãEVOHãã€ã«ã ã
50æ¥çµéåŸã«ãžâïŒâãšãã«ããã·ã«ãã¿ã¬ãŒã
38ééïŒ
å«æãã0.3mmã®è»è³ªããªå¡©åããã«ã·
ãŒãã®è¡šé¢ã«ç±ã©ãããŒã·ãšã³æ³ã§150âã®æž©åºŠ
æ¡ä»¶äžã«ã©ãããŒã·ãšã³ãããåå¥é¢ã§æ¥çå
ã枬å®ãããã該è»è³ªããªå¡©åããã«å±€ãç Žå£
ããååãªæ¥çåãæããããšã確èªããããäž
èšEVOHãã€ã«ã ã§è¢«èŠãããè»è³ªããªå¡©åã
ãã«ã·ãŒãã®EVOHé¢äžã«ç¡å¯å¡ã®ç¡¬è³ªããªå¡©
åããã«æ¿ïŒïŒcmÃïŒcmãåãïŒmmïŒãå¯çãã
ãŠçœ®ãã該硬質ããªå¡©åããã«æ¿ã«ïŒKgã®è·éã
å ããç¶æ
ã§è©²å¯å¡å€ã®æ»²åºã»ç§»è¡éã枩床70â
ã®æ¡ä»¶äžã«èª¿ã¹ãã50æéçµéåŸã硬質ããªå¡©å
ããã«æ¿ã®ééå¢å ã¯å
šãèªããããããŸã
EVOH局衚é¢ã®ãã¿ãããã¿ãããã該å¯å¡å€
滲åºã»ç§»è¡ã®é²æ¢ã¯å®å
šã§ãã€ããæ¿¡ãéå·Ÿã§æ
ããšãæäœãè¡ã€ãŠãè¡šé¢ãæãããããšãªãã
ååãªèæ°Žæ§ã瀺ãããExample 1 A 15ÎŒ thick film (unstretched film) of EVOH with an ethylene content of 31 mol% and a saponification degree of vinyl acetate component of 99.2% was coated with a gravure coater using a urethane adhesive AD-335A and a hardening agent Cat-10.
(manufactured by Toyo Morton Co., Ltd. Mixing ratio 17:1. Belongs to the above B) and maleic anhydride 1 mol% modified vinyl chloride
86 mol%-vinyl acetate 13 mol% copolymer adhesive
MPR-TM (manufactured by Nissin Chemical Co., Ltd.; belongs to A above)
Using a solution of 20% by weight toluene/methyl-ethyl ketone (weight ratio) = 1/2 of an adhesive consisting of a mixing ratio (weight) of A/B = 65/35, the coating amount was 2 g/m 2
(based on solid content) and at a temperature of 110
â for 1 minute. In order to examine the blocking properties of the obtained coated film, the coated film and the uncoated EVOH film were brought into close contact with each other under a pressure of 50 g/cm 2 , and whether the adhesion after standing for 24 hours would be a practical obstacle. I looked into it. No stickiness,
It was confirmed that there were no problems with blocking properties. The coated film also had good slip properties. The obtained coated EVOH film
Di-2-ethylhexyl phthalate after 50 days
The material was laminated onto the surface of a 0.3 mm soft polyvinyl chloride sheet containing 38% by weight at a temperature of 150° C. using a thermal lamination method. The adhesive strength was measured by T-peel, and it was confirmed that the soft polyvinyl chloride layer was destroyed and had sufficient adhesive strength. An unplasticized hard polyvinyl chloride plate (6 cm x 6 cm, thickness 2 mm) is placed in close contact with the EVOH side of the soft polyvinyl chloride sheet covered with the above EVOH film, and a load of 2 kg is applied to the hard polyvinyl chloride plate. The amount of exudation and migration of the plasticizer was measured at a temperature of 70°C.
It was investigated under the following conditions. Even after 50 hours, no increase in the weight of the rigid PVC board was observed.
No stickiness was observed on the surface of the EVOH layer, and oozing and migration of the plasticizer was completely prevented. Even if you wipe it with a wet cloth, the surface will not be damaged.
It showed sufficient water resistance.
æ¯èŒã®ãããã¡ã¿ã¢ã¯ãªã«é
žã¡ãã«86ã¢ã«ïŒ
ã
ã¡ã¿ã¢ã¯ãªã«é
žããã«14ã¢ã«ïŒ
ã®ã¢ã¯ãªã«ç³»å
±é
åäœã®åãåãã®ãã€ã«ã ã該è»è³ªããªå¡©åãã
ã«ã·ãŒãã«ç±ã©ãããŒãããŠåŸãã·ãŒããåæ§ã«
è©Šéšã«ä»ããã24æéçµéåŸã®è©²ç¡¬è³ªããªå¡©åã
ãã«æ¿ã®ééå€åã¯ã3.2ééïŒ
ã§ãã€ãã該é
éå€åã¯è©²å¯å¡å€ã®ç§»è¡ã«èµ·å ããŠããããšã確
èªããã該å
±éåäœãã€ã«ã è¡šé¢ã®ãã¿ãããèª
ããã For comparison, 86 mol% methyl methacrylate;
A sheet obtained by thermally laminating a film of the same thickness of an acrylic copolymer containing 14 mol % of butyl methacrylate to the flexible polyvinyl chloride sheet was similarly subjected to the test. The weight change of the hard polyvinyl chloride plate after 24 hours was 3.2% by weight. It was confirmed that the weight change was caused by the transfer of the plasticizer, and stickiness on the surface of the copolymer film was also observed.
ãŸãæ¯èŒã®ããã«ãADâ335A硬åå€Catâ10
ïŒæ··åæ¯17ïŒïŒïŒãŸãã¯MPRâTMãåç¬ã§æ¥ç
å€ãšããŠçšããŠãåèšã«æºããŠæ¥çå€ã³ãŒã
EVOHãã€ã«ã ãåŸããADâ335Aãšç¡¬åå€Cat
â10ã®ãŠã¬ã¿ã³ç³»æ¥çå€åç¬äœ¿çšã®ãã®ã¯ããã
ããã³ã°ãèããå®çšãé£ããã®ã§ãã€ããã¹ãª
ããæ§ãäžæºè¶³ãªãã®ã§ãã€ãããŸãMPRâ
TMåç¬äœ¿çšã®ãã®ã¯èããããã³ã°æ§ãã¹ãªã
ãæ§ã«ãããŠã¯æºè¶³ãªãã®ã§ãã€ãããç±ã©ãã
ãŒãåŸã®æ¥çåã¯0.28KgïŒ15mmã§EVOHå±€ãå¥é¢
ããäžæºè¶³ãªãã®ã§ãã€ãã For comparison, AD-335A hardener Cat-10
(Mixing ratio 17:1) or MPR-TM alone as adhesive, adhesive coat as described above.
Got EVOH film. AD-335A and hardener Cat
-10, in which a urethane adhesive was used alone, caused significant blocking and was difficult to put into practical use. The slip property was also unsatisfactory. Also MPRâ
The product using TM alone was satisfactory in terms of blocking resistance and slip property, but the adhesive strength after heat lamination was unsatisfactory as the EVOH layer peeled off at 0.28 kg/15 mm.
å®æœäŸ ïŒ
å®æœäŸïŒã«ãããŠãšãã¬ã³å«43ã¢ã«ïŒ
ãé
¢é
žã
ãã«æåã®ããå床99.3ã¢ã«ïŒ
ã®EVOHãã€ã«ã
ãçšããç±ã©ãããŒã·ãšã³çšè©²EVOHãã€ã«ã
ãåŸãŠ130âã®æž©åºŠæ¡ä»¶äžã«ç±ã©ãããŒã·ãšã³ã
è¡ã€ã以å€ã¯å®æœäŸïŒã«æºããŠè¡ãã該å¯å¡å€ã®
滲åºã»ç§»è¡ãã¹ããåæ§ã«è¡ã€ãã該ç±ã©ãããŒ
ã·ãšã³çšãã€ã«ã ã¯è¯å¥œãªèããããã³ã°æ§ã瀺
ããã¹ãªããæ§ãè¯å¥œã§ãã€ãã該硬質ããªå¡©å
ããã«æ¿ã®ééå€åã¯å
šãèªããããªãã€ãããŸ
ã該局éæ¥çåã¯å
åã§ãããæ¥çåãåå¥é¢
ã§æž¬å®ããéã該è»è³ªããªå¡©åããã«å±€ãç Žå£ã
ãã該EVOHè¡šé¢ã®è©²èæ°Žæ§ãå
åã§ãã€ããExample 2 Using the EVOH film in Example 1 with an ethylene content of 43 mol% and a saponification degree of vinyl acetate component of 99.3 mol%, the EVOH film for thermal lamination was obtained and thermal lamination was performed at a temperature of 130°C. The procedure of Example 1 was followed except for the test, and the exudation/transfer test of the plasticizer was conducted in the same manner. The film for thermal lamination exhibited good blocking resistance and good slip properties. No change in weight of the hard polyvinyl chloride board was observed. Moreover, the interlayer adhesive strength was sufficient, and when the adhesive strength was measured by T-peel, the soft polyvinyl chloride layer was destroyed. The water resistance of the EVOH surface was also sufficient.
å®æœäŸ ïŒ
ãšãã¬ã³å«é26ã¢ã«ïŒ
ãé
¢é
žããã«ã®ããå床
99.5ïŒ
ã®EVOHïŒïŒžïŒãšãšãã¬ã³å«é51ã¢ã«ïŒ
ã
é
¢é
žããã«æåã®ããå床99.3ïŒ
ã®EVOHïŒïŒ¹ïŒ
ãšãïŒå°ã®æŒåºæ©ã«äŸçµŠããïŒå±€çšïŒŽâãã€ãçš
ããŠã220âã®ãã€å
ã§æº¶èæš¹èãæ¥åãããŠã
EVOHïŒïŒžïŒå±€ã®åãã6ÎŒãEVOHïŒïŒ¹ïŒå±€ã®å
ãã9ÎŒã®è€åEVOHãã€ã«ã ãåŸãã該è€å
EVOHãã€ã«ã ã®ïŒžé¢ãè»è³ªããªå¡©åããã«ã·
ãŒãã«é£æ¥ããããã«å®æœäŸïŒã«æºããŠç±ã©ãã
ãŒã·ãšã³ãè¡ã€ããäœãæ¥çå€ãšããŠã¯ãŠã¬ã¿ã³
ç³»æ¥çå€EPSâ703Aãšè§ŠåªKPâ90ïŒå€§æ¥æ¬ã€ã³
ã瀟補ãæ··åæ¯10ïŒïŒåèšïŒ¢ã«å±ããïŒãšãå®æœ
äŸïŒã§çšããMPRâTMã®æ··åå²åïŒïŒ¢ïŒïŒ
ã®æ··åç³»æ¥çå€ãããŸãè»è³ªããªå¡©åããã«ã·ãŒ
ããšããŠã¯å¯å¡å€ãšããŠãžâïœâãªã¯ãã«ãã¿ã¬
ãŒãïŒããªâïŒâãšãã«ããã·ã«ãã¹ããšãŒãïŒ
50ïŒ50ïŒééæ¯ïŒã®æ··åç©ã35ééïŒ
å«ãè»è³ªã
ãªå¡©åããã«ã·ãŒããçšãã125âã®æž©åºŠæ¡ä»¶äž
ã«ç±ã©ãããŒã·ãšã³ãè¡ã€ããExample 3 Ethylene content 26 mol%, saponification degree of vinyl acetate
99.5% EVOH(X) and ethylene content 51 mol%,
EVOH (Y) with saponification degree of 99.3% of vinyl acetate component
and are fed to two extruders, and using a two-layer T-die, the molten resin is joined in the die at 220â,
A composite EVOH film was obtained in which the EVOH (X) layer had a thickness of 6 ÎŒm and the EVOH (Y) layer had a thickness of 9 ÎŒm. the compound
The EVOH film was thermally laminated in accordance with Example 1 so that the X side was adjacent to the soft polyvinyl chloride sheet. However, the adhesives used were urethane adhesive EPS-703A, catalyst KP-90 (manufactured by Dainippon Ink Co., Ltd., mixing ratio 10:1, belonging to B above), and MPR-TM used in Example 1 at a mixing ratio of A/ B=1
For the flexible polyvinyl chloride sheet, di-n-octyl phthalate/tri-2-ethylhexyl phosphate was used as a plasticizer.
Thermal lamination was performed at a temperature of 125° C. using a flexible polyvinyl chloride sheet containing 35% by weight of a 50/50 (weight ratio) mixture.
æ¥çå€å±€ã§è¢«èŠãããEVOHãã€ã«ã ã¯è¯å¥œ
ãªèããããã³ã°æ§ã瀺ãããŸãã¹ãªããæ§ãè¯
奜ã§ãã€ãã該EVOHãã€ã«ã ãç±ã©ãããŒã
ãããè»è³ªããªå¡©åããã«ã·ãŒãã«ã€ããŠå®æœäŸ
ïŒãšåæ§ã«ããŠå¯å¡å€ã®æ»²åºã»ç§»è¡ã®æç¡ã調ã¹
ãã該ééå€åãšãè¡šé¢ã®ãã¿ãããèªããããª
ãã€ãããŸã該局éã®æ¥çåãååã§ãããå
å¥é¢ã§æ¥çåã枬å®ããéã該ããªå¡©åããã«å±€
ãç Žå£ããã The EVOH film coated with the adhesive layer showed good blocking resistance and also good slip resistance. The soft polyvinyl chloride sheet on which the EVOH film was thermally laminated was examined in the same manner as in Example 1 to see if the plasticizer oozed out or migrated. Neither the weight change nor the surface stickiness was observed. The adhesive strength between the layers was also sufficient, and when the adhesive strength was measured by T-peel, the polyvinyl chloride layer was destroyed.
æ¯èŒã®ãããå®æœäŸïŒã§çšããã¢ã¯ãªã«å
±éå
äœã®ãã€ã«ã ãç±ã©ãããŒããã該è»è³ªããªå¡©å
ããã«ã·ãŒããåŸãŠã該滲åºã»ç§»è¡ã®æç¡ã調ã¹
ãããã«åæ§ã«ãã¹ãã«ä»ããã該硬質ããªå¡©å
ããã«æ¿ã®ééå¢å ã¯30æéçµéåŸ3.1ééïŒ
ã
ã€ãã For comparison, a flexible polyvinyl chloride sheet obtained by thermally laminating the acrylic copolymer film used in Example 1 was obtained and subjected to the same test to determine the presence or absence of oozing and migration. The weight increase of the rigid polyvinyl chloride board was 3.1% by weight after 30 hours.
ãŸãæ¯èŒã®ãããæ¥çå€ãšããŠEPSâ703ãšè§Š
åªKPâ90ïŒæ··åæ¯15ïŒïŒïŒãåç¬ã§çšãã該æ¥ç
å€å±€ã§è¢«èŠãããã³ãŒãEVOHãåŸãããèã
ãããã³ã°æ§åã³ãã¹ãªããæ§ãšãã«äžè¯ã§å®çš
ããããã®ã«ã¯è³ããªãã€ãã For comparison, EPS-703 and catalyst KP-90 (mixing ratio 15:1) were used alone as an adhesive to obtain a coated EVOH coated with the adhesive layer, but the blocking resistance and slipping resistance were Both were defective and could not be put into practical use.
å®æœäŸ ïŒ
å®æœäŸïŒã«ãããŠãšãã¬ã³å«é49ã¢ã«ïŒ
ãé
¢é
ž
ããã«æåã®ããå床99.2ïŒ
ã®äºè»žå»¶äŒžïŒé¢ç©å»¶
䌞åçïŒÃïŒåïŒãããEVOHãã€ã«ã ãçšãã
ãŸãè»è³ªããªå¡©åããã«ã·ãŒããšããŠãå¯å¡å€å¡©
çŽ åãã©ãã€ã³ïŒãžâïœâãªã¯ãã«ãã¿ã¬ãŒãïŒ
50ïŒ50ïŒééæ¯ïŒã®æ··åç©39ééïŒ
å«æãã該ã·
ãŒããããŸãæ¥çå€ãšããŠãŠã¬ã¿ã³ç³»æ¥çå€AD
â900ãšç¡¬åå€ADâRT5ïŒæ±æŽã¢ãŒãã³ç€Ÿè£œãæ··
åæ¯100ïŒ15ãåèšïŒ¢ã«å±ãããïŒãšMPRâTM
ã®50ïŒ50ïŒééæ¯ïŒã®æ··åç³»æ¥çå€ãçšãã以å€
ã¯å®æœäŸïŒãšåæ§ã«è¡ã€ãã該硬質ããªå¡©åãã
ã«æ¿ã®ééå€åãããŸãå¯å¡å€ã®è©²EVOHãã€
ã«ã è¡šé¢ãžã®æ»²åºãå
šãèªããããªãã€ãã該局
éã®æ¥çåã¯å
åã§ãããæ¥çåãåå¥é¢ã§æž¬
å®ããéã該ããªå¡©åããã«åãç Žå£ããã該
EVOHè¡šé¢ã®è©²èæ°Žæ§ãå
åã§ãã€ããExample 4 Using the biaxially stretched (area stretching ratio 3 x 3 times) EVOH film with an ethylene content of 49 mol% and a saponification degree of vinyl acetate component of 99.2% in Example 1,
In addition, as a soft polyvinyl chloride sheet, plasticizer chlorinated paraffin/di-n-octyl phthalate =
The sheet containing 39% by weight of a 50/50 (weight ratio) mixture was also used as an adhesive, urethane adhesive AD.
-900, curing agent AD-RT5 (manufactured by Toyo Morton Co., Ltd., mixing ratio 100:15, belongs to B above) and MPR-TM
Example 1 was carried out in the same manner as in Example 1, except that a 50/50 (weight ratio) mixed adhesive was used. No change in the weight of the hard polyvinyl chloride plate nor any oozing of the plasticizer onto the surface of the EVOH film was observed. The adhesion between the layers was sufficient and the polyvinyl chloride image was destroyed when the adhesion was measured by T-peel. Applicable
The water resistance of the EVOH surface was also sufficient.
æ¯èŒã®ããã«çšããå®æœäŸïŒãšåãã¢ã¯ãªã«å
±
éåäœã®ãã€ã«ã ã®å Žåã®è©²ééå€åã¯3.1éé
ïŒ
ã§ããã該ãã€ã«ã è¡šé¢ã®ãã¿ãããèªããã
ãã In the case of a film made of the same acrylic copolymer as in Example 1 used for comparison, the weight change was 3.1% by weight, and stickiness on the surface of the film was also observed.
ãŸãæ¯èŒã®ãããADâ900ãšç¡¬åå€ADâRT5
ã®ãŠã¬ã¿ã³ç³»æ¥çå€ãåç¬ã§æ¥çå€ãšããŠçšããŠ
該æ¥çå±€ãã³ãŒããããEVOHãåŸãããæ¥ç
åã¯å
åã«æºè¶³ãªãã®ïŒè©²ããªå¡©åããã«å±€ãç Ž
å£ããïŒã®è©²ã³ãŒãEVOHãã€ã«ã ã®èããã
ãã³ã°æ§ã¯ãéåžžã«äžæºè¶³ãªãã®ã§ãããå®çšã
ãããã®ãšã¯ãªããªãã€ãã For comparison, AD-900 and hardening agent AD-RT5
An EVOH film coated with the adhesive layer was obtained by using a urethane adhesive alone as an adhesive, but the adhesive strength was sufficiently satisfactory (the polyvinyl chloride layer was destroyed). The blocking resistance was extremely unsatisfactory and could not be put to practical use.
å®æœäŸ ïŒ
å®æœäŸïŒã«ãããŠãŠã¬ã¿ã³ç³»æ¥çå€ãšããŠããª
ã¬ã³ãžã€ãœã·ã¢ããŒãïŒã³ãããŒããæ¥æ¬ããª
ãŠã¬ã¿ã³å·¥æ¥ç€Ÿè£œïŒãšååéçŽ800ã®æ«ç«¯ã°ãªã³
ãŒã«ã®ããªãšã¹ãã«ã®æ··åç©ïŒæ··åæ¯ïŒééïŒ
ïŒïŒïŒïŒãçšããä»ã¯ãå®æœäŸïŒãšåæ§ã«è¡ã€
ãã該ç±ã©ãããŒã·ãšã³çšãã€ã«ã ã¯ãè¯å¥œãªè
ããããã³ã°æ§ã瀺ããŸãã¹ãªããæ§ãè¯å¥œã§ã
ã€ãã該硬質ããªå¡©åããã«æ¿ã®ééå€åã¯å
šã
èªããããªãã€ãããŸãã該局éæ¥çåã¯ãå
å
ã§ãããæ¥çåãåå¥é¢ã§æž¬å®ããéã該è»è³ª
ããªå¡©åããã«å±€ãç Žå£ããã該EVOHè¡šé¢ã®
æ±ææž
ææã®èæ°Žæ§ãå
åã§ãã€ããExample 5 In Example 1, a mixture (mixing ratio (weight)
1:2) was used in the same manner as in Example 1. The film for thermal lamination exhibited good anti-blocking properties and good slip properties. No change in weight of the hard polyvinyl chloride board was observed. Further, the interlayer adhesive strength was sufficient, and when the adhesive strength was measured by T-peel, the soft polyvinyl chloride layer was destroyed. The water resistance of the EVOH surface during cleaning was also sufficient.
å®æœäŸ ïŒ
å®æœäŸïŒã«æŒãŠå¡©åããã«ç³»æ¥çå€ãšããŠå¡©å
ããã«æå80ã¢ã«ïŒ
ãé
¢é
žããã«æå17ã¢ã«ïŒ
ã
ãšãã«ã¢ã¯ãã«é
žãšã¹ãã«æåïŒã¢ã«ïŒ
ã®å
±éå
äœãçšãã以å€ã¯ãå®æœäŸïŒãšåæ§ã«ããŠåŸãç±
ã©ãããŒã·ãšã³çšãã€ã«ã ã¯è¯å¥œãªèããããã³
ã°æ§ã瀺ããåã¹ãªããæ§ãè¯å¥œã§ãã€ãã該硬
質ããªå¡©åããã«æ¿ã®ééå€åã¯å
šãèªããããª
ãã€ãããŸãã該局éæ¥çåã¯å
åã§ãããæ¥ç
åãåå¥é¢ã§æž¬å®ããé該è»è³ªããªå¡©åããã«
å±€ãç Žå£ãããExample 6 In Example 1, the vinyl chloride adhesive contained 80 mol% of the vinyl chloride component, 17 mol% of the vinyl acetate component,
A film for thermal lamination obtained in the same manner as in Example 1 except that a copolymer containing 3 mol % of the ethyl actylic acid ester component was used showed good blocking resistance and good slip property. No change in weight of the hard polyvinyl chloride board was observed. Further, the interlayer adhesive strength was sufficient, and when the adhesive strength was measured by T-peel, the soft polyvinyl chloride layer was destroyed.
Claims (1)
ïŒ ããã³é ¢é žããã«ããã³ïŒãŸãã¯ïŒã¡ã¿ïŒã¢ã¯
ãªã«é žãšã¹ãã«æåã40ãïŒã¢ã«ïŒ å«ãå¡©åãã
ã«ç³»å ±éåäœ(A)ãšãã€ãœã·ã¢ããŒãåºãå«ãåå¿
åããªãŠã¬ã¿ã³ç³»é«åå(B)ãšããæãã該混åå²
åïŒééïŒãïŒïŒ¢ïŒ2/3ãïŒã§ããæ¥çå€å±€ã§
被èŠãããããšãã¬ã³å«é20ã60ã¢ã«ïŒ ãé ¢é žã
ãã«æåã®ããå床95ïŒ ä»¥äžã®ãšãã¬ã³âé ¢é žã
ãã«å ±éåäœããåç©ãããªãç±ã©ãããŒã·ãšã³
çšãã€ã«ã ã ïŒ ãšãã¬ã³å«éã25ã50ã¢ã«ïŒ ã§ããç¹èš±è«æ±
ã®ç¯å²ç¬¬ïŒé èšèŒã®ãã€ã«ã ã ïŒ ãšãã¬ã³âé ¢é žããã«å ±éåäœããåç©ãã€
ã«ã ã®åããïŒã50ÎŒã§ããç¹èš±è«æ±ã®ç¯å²ç¬¬ïŒ
é ãŸãã¯ç¬¬ïŒé èšèŒã®ãã€ã«ã ã ïŒ ãšãã¬ã³âé ¢é žããã«å ±éåäœããåç©ãã€
ã«ã ããšãã¬ã³å«é20ã35ã¢ã«ïŒ ã®è©²ããåç©å±€
ãšãšãã¬ã³å«é40ã60ã¢ã«ïŒ ã®è©²ããåç©å±€ã®ïŒ
å±€ãããªãããã€åè ã該æ¥çå€å±€ã«é£æ¥ããŠãª
ãç¹èš±è«æ±ã®ç¯å²ç¬¬ïŒé ãªãã第ïŒé ã®ãã¥ãã
ã«èšèŒã®ãã€ã«ã ã ïŒ å¯å¡åããªå¡©åããã«ãã€ã«ã ãŸãã¯ã·ãŒã
ãžã®ç±ã©ãããŒã·ãšã³çšã§ããç¹èš±è«æ±ã®ç¯å²ç¬¬
ïŒé ãªãã第ïŒé ã®ãã¥ããã«èšèŒã®ãã€ã«ã ã[Scope of Claims] 1. A vinyl chloride copolymer (A) in which one of its surfaces contains 60 to 99 mol% of vinyl chloride component and 40 to 1 mol% of vinyl acetate and/or (meth)acrylic acid ester component. and a reactive polyurethane polymer (B) containing an isocyanate group, the adhesive layer having an ethylene content of 20 to 60 and covered with an adhesive layer having a mixing ratio (weight) of A/B = 2/3 to 6. A film for thermal lamination comprising a saponified ethylene-vinyl acetate copolymer having a saponification degree of vinyl acetate component of 95% or more by mole. 2. The film according to claim 1, having an ethylene content of 25 to 50 mol%. 3. Claim 1, wherein the saponified ethylene-vinyl acetate copolymer film has a thickness of 5 to 50ÎŒ.
The film according to item 1 or 2. 4 The ethylene-vinyl acetate copolymer saponified film has two saponified layers, one having an ethylene content of 20 to 35 mol% and the other having an ethylene content of 40 to 60 mol%.
4. A film according to any one of claims 1 to 3, comprising a layer, the former being adjacent to the adhesive layer. 5. The film according to any one of claims 1 to 4, which is used for thermal lamination to a plasticized polyvinyl chloride film or sheet.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9736284A JPS60239233A (en) | 1984-05-14 | 1984-05-14 | Film for thermal lamination |
CA000480920A CA1245145A (en) | 1984-05-14 | 1985-05-07 | Heat-laminating composite film and laminated material using the same |
US06/731,927 US4684564A (en) | 1984-05-14 | 1985-05-08 | Heat-laminating composite film and laminated material using the same |
DE8585105882T DE3567893D1 (en) | 1984-05-14 | 1985-05-13 | Heat-laminatable composite film and laminated material using the same |
EP19850105882 EP0164594B1 (en) | 1984-05-14 | 1985-05-13 | Heat-laminatable composite film and laminated material using the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9736284A JPS60239233A (en) | 1984-05-14 | 1984-05-14 | Film for thermal lamination |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60239233A JPS60239233A (en) | 1985-11-28 |
JPH0376663B2 true JPH0376663B2 (en) | 1991-12-06 |
Family
ID=14190387
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9736284A Granted JPS60239233A (en) | 1984-05-14 | 1984-05-14 | Film for thermal lamination |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60239233A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1950036A4 (en) | 2005-11-15 | 2008-11-19 | Toray Industries | Matte multilayer polyester film |
-
1984
- 1984-05-14 JP JP9736284A patent/JPS60239233A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS60239233A (en) | 1985-11-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2007163C (en) | Pressure-sensitive film composite having improved adhesion to plasticized vinyl substrates | |
US4855181A (en) | Laminate with a blend layer of polyesteramide and ethylene-vinyl acetate copolymer | |
EP0164594B1 (en) | Heat-laminatable composite film and laminated material using the same | |
CA2120608A1 (en) | Microporous pressure sensitive adhesive coated sheeting | |
USH1982H1 (en) | Primer coated amorphous plastic films | |
JPH0376663B2 (en) | ||
JPS60195146A (en) | Composition for semirigid vinyl chloride resin moldings | |
JP5054287B2 (en) | Antifouling film for wallpaper | |
JPH0416340B2 (en) | ||
JPH0456744B2 (en) | ||
JP6789870B2 (en) | Laminates, wallpaper and wall structures | |
JPH11961A (en) | Surface protective film or sheet | |
JP4181920B2 (en) | Antifouling film for wallpaper | |
JP3634515B2 (en) | Antistatic barrier film | |
JP2006097201A (en) | Interior material | |
JP3148462B2 (en) | Laminate | |
JP4327576B2 (en) | Polyvinyl chloride base material | |
JP3815849B2 (en) | Laminated body | |
JP3781507B2 (en) | Laminated body | |
JPH075774B2 (en) | Manufacturing method of laminated body | |
JP2544753B2 (en) | Polyvinyl chloride laminated structure | |
JP2017196775A (en) | Moisture-proof film applicable to building material | |
JP2020078944A (en) | Moisture-proof film applicable to building material | |
JP3029752B2 (en) | Laminated film and its use | |
JP3097266B2 (en) | Print laminate |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
LAPS | Cancellation because of no payment of annual fees |