JP4128419B2 - Biaxially stretched polypropylene multilayer film and method for producing the same - Google Patents
Biaxially stretched polypropylene multilayer film and method for producing the same Download PDFInfo
- Publication number
- JP4128419B2 JP4128419B2 JP2002282202A JP2002282202A JP4128419B2 JP 4128419 B2 JP4128419 B2 JP 4128419B2 JP 2002282202 A JP2002282202 A JP 2002282202A JP 2002282202 A JP2002282202 A JP 2002282202A JP 4128419 B2 JP4128419 B2 JP 4128419B2
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- Prior art keywords
- layer
- acrylic
- biaxially stretched
- meth
- multilayer film
- 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
- 229920001155 polypropylene Polymers 0.000 title claims description 87
- -1 polypropylene Polymers 0.000 title claims description 66
- 239000004743 Polypropylene Substances 0.000 title claims description 58
- 238000004519 manufacturing process Methods 0.000 title description 5
- 239000011347 resin Substances 0.000 claims description 42
- 229920005989 resin Polymers 0.000 claims description 42
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 41
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 31
- 229920006378 biaxially oriented polypropylene Polymers 0.000 claims description 9
- 239000011127 biaxially oriented polypropylene Substances 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 5
- 239000010410 layer Substances 0.000 description 61
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 15
- 239000004925 Acrylic resin Substances 0.000 description 10
- 229920000178 Acrylic resin Polymers 0.000 description 10
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000005026 oriented polypropylene Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 6
- 230000002441 reversible effect Effects 0.000 description 6
- 230000008018 melting Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 239000005022 packaging material Substances 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical group CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 150000002430 hydrocarbons Chemical group 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- NIDNOXCRFUCAKQ-UHFFFAOYSA-N bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2C(O)=O NIDNOXCRFUCAKQ-UHFFFAOYSA-N 0.000 description 2
- 239000002981 blocking agent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- ZKECVHXIVHRIIA-UHFFFAOYSA-N n-(2,2,6,6-tetramethylpiperidin-1-yl)prop-2-enamide Chemical compound CC1(C)CCCC(C)(C)N1NC(=O)C=C ZKECVHXIVHRIIA-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- GIIUJJXXMYYQQD-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-1-yl) prop-2-enoate Chemical compound CC1(C)CCCC(C)(C)N1OC(=O)C=C GIIUJJXXMYYQQD-UHFFFAOYSA-N 0.000 description 1
- FISZAKVDTCHVGC-UHFFFAOYSA-N (2-butoxyphenyl)-phenylmethanone Chemical compound CCCCOC1=CC=CC=C1C(=O)C1=CC=CC=C1 FISZAKVDTCHVGC-UHFFFAOYSA-N 0.000 description 1
- TXVIUQWYJKHWBD-UHFFFAOYSA-N (2-ethoxyphenyl)-[4-(2-hydroxyethoxy)phenyl]methanone Chemical compound C(C)OC1=C(C(=O)C2=CC=C(C=C2)OCCO)C=CC=C1 TXVIUQWYJKHWBD-UHFFFAOYSA-N 0.000 description 1
- RFWYJPXOKLPVND-UHFFFAOYSA-N (2-ethoxyphenyl)-phenylmethanone Chemical compound CCOC1=CC=CC=C1C(=O)C1=CC=CC=C1 RFWYJPXOKLPVND-UHFFFAOYSA-N 0.000 description 1
- WLQXEFXDBYHMRG-UPHRSURJSA-N (z)-4-(oxiran-2-ylmethoxy)-4-oxobut-2-enoic acid Chemical compound OC(=O)\C=C/C(=O)OCC1CO1 WLQXEFXDBYHMRG-UPHRSURJSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 1
- 229940018557 citraconic acid Drugs 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920006228 ethylene acrylate copolymer Polymers 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003921 oil Substances 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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 235000011888 snacks Nutrition 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、二軸延伸ポリプロピレンフィルム層とアクリル系紫外線吸収樹脂層との接着性、特に高湿度下で処理した後の接着強度に優れ、且つ紫外線遮断性を有する包装用材料として好適な二軸延伸ポリプロピレン多層フィルムに関する。
【０００２】
【従来の技術】
二軸延伸ポリプロピレンフィルム（以下ＯＰＰフィルムと呼ぶことがある）は、その優れた透明性、機械的強度、剛性等を活かして包装材料をはじめ広い分野で使用されている。中でも、食品、化粧品、医薬品等の包装材料として用いる場合は、被包装物の劣化を防ぐために、ＯＰＰフィルムに酸素透過度や水蒸気透過度を少なくするためのガスバリヤー層、あるいは紫外線を遮断する層等を積層して多層化して用いられている。かかる紫外線遮断層の一つとしてアクリル系紫外線吸収樹脂層を積層することが提案されている。そして、ＯＰＰフィルムはそれ自体極性基を有しないことから、単にＯＰＰフィルムとアクリル系紫外線吸収樹脂層とを積層しても接着性に劣ることから、例えば、紫外線吸収型アクリル系樹脂に熱接着性樹脂を混合したものを積層すること（特開平９−３００５４１号公報）、紫外線吸収型アクリル系樹脂にカチオン系ポリマーを混合したものを積層すること（特開平７−２１４７３２号公報）等が提案されている。又、紫外線吸収型アクリル系樹脂を用いる例ではないが、ポリオレフィン層とアクリル樹脂層との接着性を改良する方法として、接着層としてエチレン─アクリル酸エステル共重合体と不飽和カルボン酸変性ポリオレフィン等との組成物を用いること（特開平６−２５５０４８号公報）が提案されている。
【０００３】
しかしながら、何れの方法も、ＯＰＰフィルムと紫外線吸収型アクリル系樹脂層との接着強度を改良するために、紫外線吸収型アクリル系樹脂に不飽和カルボン酸変性ポリオレフィン等の接着性改質材を混合しており、紫外線吸収型アクリル系樹脂本来の紫外線遮断性を十分発揮できない場合がある。又、ＯＰＰフィルムと紫外線吸収型アクリル系樹脂層との間の接着性を改良するには、予めにＯＰＰフィルムの表面にウレタン樹脂等でアンカーコートをしておく必要があるし、得られるＯＰＰフィルムと紫外線吸収型アクリル系樹脂層との間の接着強度も、高湿度下で処理した後に低下する虞がある。
【０００４】
【発明が解決しようとする課題】
そこで、本発明は、アンカーコート等の前処理を必要とすることなく、二軸延伸ポリプロピレンフィルム層とアクリル系紫外線吸収樹脂層との接着性、特に高湿度下で処理した後にも優れた二軸延伸ポリプロピレン多層フィルムを得ることを目的とした。
【０００５】
【課題を解決するための手段】
【発明の概要】
本発明は、ポリプロピレンと変性プロピレン重合体（Ａ）とを共押出し成形してシートを得た後、当該シートを縦方向に延伸し、ついで、変性プロピレン重合体（Ａ）層上にアクリル系紫外線吸収樹脂（Ｂ）を被覆した後、横方向に延伸することにより、二軸延伸ポリプロピレンフィルムの片面に、変性プロピレン重合体（Ａ）層を介してアクリル系紫外線吸収樹脂（Ｂ）層が積層されてなることを特徴とする二軸延伸ポリプロピレン多層フィルムを提供することにある。
【０００６】
ポリプロピレンと変性プロピレン重合体（Ａ）とを共押出し成形してシートを得た後、当該シートを縦方向に延伸し、ついで、変性プロピレン重合体（Ａ）層上にアクリル系紫外線吸収樹脂（Ｂ）を被覆した後、横方向に延伸することを特徴とする二軸延伸ポリプロピレン多層フィルムの製造方法を提供することにある。
【０００７】
【発明の具体的な説明】
二軸延伸ポリプロピレンフィルム
本発明に係わる二軸延伸ポリプロピレンフィルムは、一般に製造・販売されている公知のフィルムであり、プロピレンの単独重合体、若しくはプロピレンと少量、通常５モル％以下のエチレン、１−ブテン、１−ヘキセン、４−メチル・１−ペンテン、１−オクテン等のα―オレフィンとの共重合体を逐次あるいは同時にニ軸延伸して得られるフィルムである。
【０００８】
変性プロピレン重合体（Ａ）
本発明に係わる変性プロピレン重合体（Ａ）は、プロピレンの単独重合体、若しくはプロピレンとエチレン、１−ブテン、１−ヘキセン、４−メチル・１−ペンテン、１−オクテン等のα―オレフィンとのプロピレンを主体とした共重合体に極性基を付与して変性したものである。中でも、不飽和カルボン酸もしくはその誘導体でグラフト変性したものが、二軸延伸ポリプロピレンフィルムと後述のアクリル系紫外線吸収樹脂（Ｂ）層との接着性の改善効果に優れるので好ましい。
【０００９】
不飽和カルボン酸もしくはその誘導体としては、例えばアクリル酸、マレイン酸、フマール酸、テトラヒドロフタル酸、イタコン酸、シトラコン酸、クロトン酸、イソクロトン酸、ナジック酸（エンドシス−ビシクロ［２.２.１］ヘプト−５−エン−２,３−ジカルボン酸）等の不飽和カルボン酸；またはその誘導体、例えば酸ハライド、アミド、イミド、無水物、エステル等が挙げられる。かかる誘導体の具体例としては、例えば塩化マレニル、マレイミド、無水マレイン酸、無水シトラコン酸、マレイン酸モノメチル、マレイン酸ジメチル、グリシジルマレエート等が挙げられる。これらの中では、不飽和ジカルボン酸またはその酸無水物が好適であり、特にマレイン酸、ナジック酸またはこれらの酸無水物が好ましく用いられる。
【００１０】
不飽和カルボン酸もしくはその誘導体でグラフト変性された変性プロピレン重合体は、好ましくは変性前のプロピレン重合体に基づいて０.０５〜１５重量％、より好ましくは０.１〜１０重量％の不飽和カルボン酸もしくはその誘導体でグラフト変性されている。また、変性プロピレン重合体は、好ましくはメルトフローレート（ＭＦＲ、２３０℃）０.１〜５０ｇ／１０分、より好ましくはＭＦＲ０.３〜３０ｇ／１０分を示す。
【００１１】
アクリル系紫外線吸収樹脂（Ｂ）
本発明に係わるアクリル系紫外線吸収樹脂（Ｂ）は、共重合成分として、紫外線吸収機能を有するベンゾトリアゾール基、ベンゾフェノン基等の紫外線吸収基が結合した（メタ）アクリル酸エステル（Ｃ）とその他の（メタ）アクリル酸エステル（Ｄ）との共重合体である。
（メタ）アクリル酸エステル（Ｃ）は、下記一般式（１）で表される化合物である。
ＣＨ２＝ＣＲ1（ＣＯＯＲ２） （１）
（Ｒ1は、水素原子またはメチル基を示し、Ｒ２は紫外線吸収基を含む炭化水素基を示す。）
かかる（メタ）アクリル酸エステル（Ｃ）の具体例としては、紫外線吸収基がベンゾトリアゾール基の場合は、例えば、２−［２’−ヒドロキシ−５’−（メタ）アクリロイルオキシメチルフェニル］−２Ｈ−ベンゾトリアゾール、２−［２’−ヒドロキシ−５’−（メタ）アクリロイルオキシエチルフェニル］−２Ｈ−ベンゾトリアゾール、２−［２’−ヒドロキシ−５’−（メタ）アクリロイルオキシプロピルフェニル］−２Ｈ−ベンゾトリアゾール、２−［２’−ヒドロキシ−３’−ｔｅｒｔ−ブチル−５’−（メタ）アクリロイルオキシエチルフェニル］−２Ｈ−ベンゾトリアゾール、２−［２’−ヒドロキシ−５’−ｔｅｒｔ−ブチル−３’−（メタ）アクリロイルオキシエチルフェニル］−２Ｈ−ベンゾトリアゾール等が挙げられる。
【００１２】
また、紫外線吸収基がベンゾフェノン基の場合は、例えば、２−ヒドロキシ−４−［２−（メタ）アクリロイルオキシ］エトキシベンゾフェノン、２−ヒドロキシ−４−［２−（メタ）アクリロイルオキシ］ブトキシベンゾフェノン、２−ヒドロキシ−４−［２−（メタ）アクリロイルオキシ］エトキシ−４’−（２−ヒドロキシエトキシ）ベンゾフェノン等が挙げられる。
（メタ）アクリル酸エステル（Ｄ）は、一般式（２）で表される化合物である。
ＣＨ２＝ＣＲ３（ＣＯＯＲ４） （２）
（Ｒ３は水素原子またはメチル基を示し、Ｒ４は水素原子であるか、または炭素数１〜９の炭化水素基、あるいは官能基を含む炭化水素基、もしくは紫外線安定基を含む炭化水素基を示す。）
（メタ）アクリル酸エステル（Ｄ）の具体例としては、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、メチルシクロヘキシル（メタ）アクリレート、ラウリル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソボルニル（メタ）アクリレート、ベンジル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、４−（メタ）アクリロイルオキシ−２，２，６、６−テトラメチルピペリジン、４−（メタ）アクリロイルアミノ−２，２，６、６−テトラメチルピペリジン、１−（メタ）アクリロイル−４（メタ）アクリロイルアミノ−２，２，６，６−テトラメチルピペリジン、１−（メタ）アクリロイル−４−シアノ−４（メタ）アクリロイルアミノ−２，２，６，６−テトラメチルピペリジン等が挙げられる。かかる（メタ）アクリル酸エステル（Ｄ）は、１種または２種以上を用いてもよい。
【００１３】
本発明に係わるアクリル系紫外線吸収樹脂（Ｂ）における紫外線吸収機能を有するベンゾトリアゾール基、ベンゾフェノン基等の紫外線吸収基が結合した（メタ）アクリル酸エステル（Ｃ）の割合は、その他の（メタ）アクリル酸エステル（Ｄ）を１００重量部とした場合、１０〜１５０重量部の範囲にある。（メタ）アクリル酸エステル（Ｃ）の量が１０重量部未満では、二軸延伸ポリプロピレン多層フィルムにした場合に、十分な紫外線防止効果が得られない場合があり、一方、１５０重量部を越えると塗膜の凝集力が低下したり、透明性が損なわれたりする虞がある。
本発明に係わるアクリル系紫外線吸収樹脂（Ｂ）の製造方法としては、特に限定されず従来公知の重合方法を採用することができ、例えば乳化重合、溶液重合、懸濁重合等の方法が挙げられる。
【００１４】
本発明に係わるアクリル系紫外線吸収樹脂（Ｂ）には、その作用を阻害しない範囲で、必要に応じてアクリル系紫外線吸収樹脂以外の重合体を１種または２種以上含んでいても良い。このようなアクリル系紫外線吸収樹脂以外の重合体としては、特に限定されず、例えば、ポリ塩化ビニル樹脂、ポリエステル樹脂、アクリル樹脂、ウレタン樹脂、シリコン樹脂等の熱可塑性樹脂及び熱硬化性樹脂が挙げられる。
また、上記アクリル系紫外線吸収樹脂（Ｂ）には、１種または２種以上の架橋剤を添加することもできる。架橋剤としては、イソシアネート系等、特に限定されず、添加量はアクリル系紫外線吸収樹脂（Ｂ）の作用を阻害しない範囲で、添加することができる。
【００１５】
本発明のアクリル系紫外線吸収樹脂（Ｂ）は、二軸延伸ポリプロピレンフィルムの表面に塗布するために、分散体が好ましく、分散媒体としては、コスト、作業環境面から水が好ましい。それら水性分散体の固形分濃度は通常１〜６０％重量であり、好ましくは５〜５０重量％である。分散体の固形分濃度が１％重量未満では、一定の塗膜厚みを得るために厚塗りが必要となり生産性が低下する虞があり、また濡れ性も低下する虞がある。一方６０％重量を越えたものは、粘度が高く塗布ムラが生じる虞がある。
また、水性分散体には必要に応じて滑剤、スリップ剤、アンチ・ブロッキング剤、帯電防止剤、防曇剤、顔料、染料、無機また有機の充填剤等の各種添加剤を本発明の目的を損なわない範囲で添加してもよい。
【００１６】
二軸延伸ポリプロピレン多層フィルム
本発明の二軸延伸ポリプロピレン多層フィルムは、二軸延伸ポリプロピレンフィルムの片面に、変性プロピレン重合体（Ａ）層を介してアクリル系紫外線吸収樹脂（Ｂ）層が積層されてなる。変性プロピレン重合体（Ａ）層を介することにより、アクリル系紫外線吸収樹脂（Ｂ）層を二軸延伸ポリプロピレン層に強く接着することができるが、アクリル系紫外線吸収樹脂（Ｂ）層を変性プロピレン重合体（Ａ）層上に積層した後に変性プロピレン重合体（Ａ）層とともに延伸することにより、高湿度下においても接着力が強い二軸延伸ポリプロピレン多層フィルムとなる。
二軸延伸ポリプロピレン多層フィルムにおける各層の厚さは、用途に応じて種々決められるが、通常 二軸延伸ポリプロピレンフィルムの厚さが１０〜１００μｍ、好ましくは１５〜６０μｍ、変性プロピレン重合体（Ａ）層の厚さが０．２〜１０μｍ、好ましくは０．５〜５μｍ、アクリル系紫外線吸収樹脂（Ｂ）層の厚さが０．３μｍ〜２０μｍ、好ましくは０．５μｍ〜１０μｍ、さらには０．８μｍ〜５μｍの範囲にある。
本発明の二軸延伸ポリプロピレン多層フィルムは、通常、３７０ｎｍの紫外線透過率を３０％以下、より好ましくは２０％以下、さらに好ましくは１０％以下にしておくことが望ましい。３７０ｎｍの紫外線透過率をかかる範囲にすることにより、食品等の内容物の変質や、印刷物の変色等の紫外線による悪影響を抑制することができる。３７０ｎｍの紫外線透過率が３０％を越えるとこれらの作用が十分ではなくなる虞がある。
【００１７】
二軸延伸ポリプロピレン多層フィルムの製造方法
本発明の二軸延伸ポリプロピレン多層フィルムの製造方法は、ポリプロピレンと変性プロピレン重合体（Ａ）とを共押出し成形してシートを得た後、変性プロピレン重合体（Ａ）層上に、アクリル系紫外線吸収樹脂（Ｂ）を被覆した後、当該積層シートを延伸する方法、あるいはポリプロピレンと変性プロピレン重合体（Ａ）とを共押出し成形してシートを得た後、当該シートを縦方向に延伸し、変性プロピレン重合体（Ａ）層上にアクリル系紫外線吸収樹脂（Ｂ）を被覆した後、横方向に延伸する方法である。
未延伸の積層シートあるいは縦延伸後の変性プロピレン重合体（Ａ）上にアクリル系紫外線吸収樹脂（Ｂ）を被覆する方法は、例えば、エアーナイフコーター、ダイレクトグラビアコーター、グラビアオフセット、アークグラビアコーター、グラビアリバースおよびジェットノズル方式等のグラビアコーター、トップフィードリバースコーター、ボトムフィードリバースコーターおよびノズルフィードリバースコーター等のリバースロールコーター、５本ロールコーター、リップコーター、バーコーター、バーリバースコーター、ダイコーター等種々公知の塗工機を用いて、アクリル系紫外線吸収樹脂（Ｂ）分散体中の固形分の量で３〜２００ｇ／ｍ２、好ましくは５〜１００ｇ／ｍ２となるよう塗布した後、５０〜１４０℃の温度で乾燥することにより得られる。アクリル系紫外線吸収樹脂（Ｂ）分散体中を塗布する面、すなわち、変性プロピレン重合体（Ａ）はアクリル系紫外線吸収樹脂（Ｂ）との濡れ性を改良するために予めコロナ処理等を行っておいてもよい。
二軸延伸ポリプロピレン多層フィルムの延伸温度及び延伸倍率は、通常行われている条件、例えば、同時二軸延伸であれば、延伸温度を１５０〜１９０℃、延伸倍率を縦・横各々３〜１０倍の範囲で、逐次二軸延伸であれば、縦延伸温度を１２５〜１４５℃、延伸倍率を４．５〜６倍の範囲で、アクリル系紫外線吸収樹脂（Ｂ）を塗布・乾燥した後の横延伸温度を１５０〜１９０℃、延伸倍率を９〜１１倍の範囲にして延伸すればよい。
【００１８】
【発明の効果】
本発明の二軸延伸ポリプロピレン多層フィルムは、アクリル系紫外線吸収樹脂層が二軸延伸ポリプロピレン層に強固に接着している。更に、本発明の方法で得られる二軸延伸ポリプロピレン多層フィルムは、高湿度下においても二軸延伸ポリプロピレン層とアクリル系紫外線吸収樹脂層との間の接着力が維持される。したがって、本発明の二軸延伸ポリプロピレン多層フィルムは、二軸延伸ポリプロピレンフィルム本来の特徴である透明性、機械的強度、剛性等の特徴に加え、紫外線防止性を有するので、紫外線により変化を起こす内容物、例えばスナックや菓子類などの油脂食品、化粧品、医薬品、色素の褪色を嫌う食品類及び衣料品等の包装材料として好適に使用することができる。また、ガスバリア性や水蒸気バリア性を備えた層、例えばエチレン・ビニルアルコール共重合体層、ポリビニルアルコール層、酸化アルミニウム蒸着層、酸化珪素蒸着層を備えた層を積層することにより、従来アルミ箔等で遮光を必要とした包装に対しても、中身の認識が可能な包装材料として利用することができる。さらに産業材用としては、ポスター、メニュー表、本やバインダーの表紙、掲示物、案内板等の表面にラミネートして印刷物の変色及び基材の劣化を抑制する保護用フィルムとして使用できる。
【００１９】
【実施例】
次に本発明を実施例によりさらに具体的に説明するが、本発明はこれら実施例により何等限定されるものではない。
【００２０】
実施例１
融点：１６２℃、ＭＦＲ：２ｇ／１０分のポリプロピレンを基材層とし、その片面に融点：１６５℃、ＭＦＲ：３ｇ／１０分の無水マレイン酸でグラフト変性した変性ポリプロピレンを共押し出しして得た多層フィルムを縦方向に５倍に延伸した後、変性ポリプロピレン層面に、アクリル系紫外線吸収樹脂及びアンチ・ブロッキング剤（平均粒径１．２μｍのポリメチルメタクリレート粒子）０．１重量部を含む紫外線吸収性アクリルポリマーエマルジョン（サイデン化学社製：商品名 サイビノールＸ−５０１−５１０Ｅ−１ 濃度：４０重量％）グラビアロールにて２０ｃｃコートした後、乾燥した。ついで１６０℃の熱風を循環させたテンター内で横方向に１０倍に延伸した後、１５０℃で５秒間熱風固定して二軸延伸ポリプロピレン多層フィルムを得た。得られた多層フィルムの各層の厚さはポリプロピレンフィルム基材層が２０μｍ、変性ポリプロピレン層が１μｍ、アクリル系紫外線吸収樹脂層が０．８μｍであった。
得られた二軸延伸ポリプロピレン多層フィルムを以下の方法で評価した。
【００２１】
（１）アクリル系紫外線吸収樹脂層の密着性試験（剥離強度）
厚さ５０μｍの線状低密度ポリエチレンフィルム（東セロ社製：商品名 ＴＵＸ ＦＣＤ＃５０）のコロナ処理面に、ポリウレタン系ドライラミネート用接着剤（三井武田ケミカル社製：商品名 タケラックＡ３１０：タケネートＡ３を１２：１で混合し、酢酸エチルで希釈した液）を用い２．５ｇ／ｍ２塗布した後、二軸延伸ポリプロピレン多層フィルムのアクリル系紫外線吸収樹脂とラミネートした。ラミネートした積層フィルムを４０℃で２４時間エージングした後、二軸延伸ポリプロピレン多層フィルムとポリエチレンフィルム間を剥離速度３００ｍｍ／分で剥離させ、その強度を測定した。又、４０℃で２４時間エージングした積層フィルムを孵卵器中（４０℃、９０％ＲＨ）で２４時間放置後、同様に剥離速度３００ｍｍ／分で剥離強度を測定した。
（２）紫外線吸収性
日本分光工業株式会社製分光光度計Ｕｂｅｓｔ−３５型を使用し、二軸延伸ポリプロピレン多層フィルム１枚の波長３２０ｎｍの吸収率を測定した。
二軸延伸ポリプロピレン多層フィルムの測定結果を表１に示す。
【００２２】
比較例１
実施例１で用いた変性ポリプロピレンに代えて、融点：１６２℃、ＭＦＲ：２ｇ／１０分のポリプロピレンを用いる以外は、実施例１と同様に行い二軸延伸ポリプロピレン積層フィルムを得た。得られた積層フィルムを実施例１と同様に評価した。測定結果を表１に示す。
【００２３】
比較例２
融点：１６２℃、ＭＦＲ：２ｇ／１０分のポリプロピレンを中間層とし、その片面に融点：１６５℃、ＭＦＲ：３ｇ／１０分の無水マレイン酸でグラフト変性された変性ポリプロピレンを積層した共押し出し多層フィルムを縦方向に５ 倍に延伸した後、１６０℃の熱風を循環させたテンター内で横方向に１０倍に延伸した後、１５０℃で５秒間熱固定し、さらに変性ポリプロピレン積層面にコロナ処理を行って濡れ張力３８ダインの二軸延伸ポリプロピレン積層フィルムを得た。このコロナ処理した変性ポリプロピレン層上に、実施例１で使用した紫外線吸収性アクリルポリマーエマルジョン（濃度：２０重量％）を４ｃｃコートし乾燥して、二軸延伸ポリプロピレン積層フィルムを得た。得られた積層フィルムの各層の厚さは、ポリプロピレン層が２０μｍ、変性ポリプロピレン層が１μｍで、アクリル系紫外線吸収樹脂層が０．８μｍであった。得られた積層フィルムを実施例１と同様に評価した。測定結果を表１に示す。
【００２４】
【表１】
表１ から明らかなように、実施例１で得た二軸延伸ポリプロピレン多層フィルムは、比較例１で得た二軸延伸ポリプロピレン多層フィルムに較べ初期の剥離強度が大きく、高湿度下で処理した後の剥離強度の低下もない。比較例２ で得た二軸延伸ポリプロピレン多層フィルムは初期の剥離強度は優れるものの、高湿度下で処理した後の剥離強度は低下する。したがって、二軸延伸ポリプロピレン層に変性プロピレン重合体層を設けることにより、アクリル系紫外線吸収樹脂層との接着強度は改良されるが、二軸延伸ポリプロピレン層と変性プロピレン重合体層とを縦延伸後に変性プロピレン重合体層上にアクリル系紫外線吸収樹脂層を被覆して横延伸することにより、耐高湿度性に優れた二軸延伸ポリプロピレン多層フィルムが得られる。[0001]
BACKGROUND OF THE INVENTION
The present invention is a biaxial material suitable for a packaging material having excellent adhesive strength between a biaxially stretched polypropylene film layer and an acrylic UV-absorbing resin layer, in particular, adhesive strength after processing under high humidity, and having UV blocking properties. The present invention relates to a stretched polypropylene multilayer film.
[0002]
[Prior art]
Biaxially stretched polypropylene films (hereinafter sometimes referred to as OPP films) are used in a wide range of fields including packaging materials by taking advantage of their excellent transparency, mechanical strength, rigidity and the like. In particular, when used as packaging materials for foods, cosmetics, pharmaceuticals, etc., a gas barrier layer for reducing oxygen permeability and water vapor permeability, or a layer for blocking ultraviolet rays in an OPP film, in order to prevent deterioration of the package. Etc. are laminated to form a multilayer. It has been proposed to laminate an acrylic ultraviolet absorbing resin layer as one of such ultraviolet blocking layers. Since the OPP film itself does not have a polar group, even if the OPP film and the acrylic ultraviolet absorbing resin layer are simply laminated, the adhesiveness is inferior. Laminating a mixture of resin (Japanese Patent Laid-Open No. 9-300541), laminating a mixture of a UV-absorbing acrylic resin and a cationic polymer (Japanese Patent Laid-Open No. 7-214732) and the like have been proposed. ing. Although not an example of using an ultraviolet absorbing acrylic resin, as a method for improving the adhesion between the polyolefin layer and the acrylic resin layer, an ethylene-acrylate copolymer and an unsaturated carboxylic acid-modified polyolefin are used as the adhesive layer. It has been proposed to use a composition of JP-A-6-255048.
[0003]
However, in either method, in order to improve the adhesive strength between the OPP film and the UV-absorbing acrylic resin layer, an adhesive modifier such as unsaturated carboxylic acid-modified polyolefin is mixed with the UV-absorbing acrylic resin. In some cases, the ultraviolet ray-absorbing acrylic resin inherent ultraviolet blocking property cannot be sufficiently exhibited. Also, in order to improve the adhesion between the OPP film and the UV-absorbing acrylic resin layer, it is necessary to previously coat the surface of the OPP film with urethane resin or the like, and the resulting OPP film There is also a possibility that the adhesive strength between the UV-absorbing acrylic resin layer and the UV-absorbing acrylic resin layer also decreases after the treatment under high humidity.
[0004]
[Problems to be solved by the invention]
Therefore, the present invention does not require pretreatment such as anchor coating, and is excellent in adhesion between the biaxially stretched polypropylene film layer and the acrylic ultraviolet absorbing resin layer, particularly after treatment under high humidity. The purpose was to obtain a stretched polypropylene multilayer film.
[0005]
[Means for Solving the Problems]
SUMMARY OF THE INVENTION
In the present invention, after a polypropylene and a modified propylene polymer (A) are coextruded to obtain a sheet, the sheet is stretched in the longitudinal direction, and then acrylic ultraviolet rays are formed on the modified propylene polymer (A) layer. After coating the absorbent resin (B), the acrylic ultraviolet absorbing resin (B) layer is laminated on one side of the biaxially stretched polypropylene film via the modified propylene polymer (A) layer by stretching in the transverse direction. An object of the present invention is to provide a biaxially stretched polypropylene multilayer film.
[0006]
After coextrusion molding of polypropylene and the modified propylene polymer (A) to obtain a sheet, the sheet is stretched in the longitudinal direction, and then an acrylic ultraviolet absorbing resin (B) is formed on the modified propylene polymer (A) layer. ) Is then stretched in the transverse direction, and a method for producing a biaxially stretched polypropylene multilayer film is provided.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Biaxially stretched polypropylene film The biaxially stretched polypropylene film according to the present invention is a known film that is generally produced and sold, and is a homopolymer of propylene or a small amount of propylene and usually 5 mol% or less. It is a film obtained by biaxially stretching a copolymer with an α-olefin such as ethylene, 1-butene, 1-hexene, 4-methyl / 1-pentene and 1-octene sequentially or simultaneously.
[0008]
Modified propylene polymer (A)
The modified propylene polymer (A) according to the present invention is a homopolymer of propylene, or propylene and an α-olefin such as ethylene, 1-butene, 1-hexene, 4-methyl / 1-pentene, 1-octene. A copolymer mainly composed of propylene is modified by adding a polar group. Among them, those graft-modified with an unsaturated carboxylic acid or a derivative thereof are preferable because they are excellent in improving the adhesiveness between the biaxially stretched polypropylene film and the acrylic ultraviolet absorbing resin (B) layer described later.
[0009]
Examples of the unsaturated carboxylic acid or its derivative include acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid (endocis-bicyclo [2.2.1] hept Unsaturated carboxylic acids such as -5-ene-2,3-dicarboxylic acid); or derivatives thereof such as acid halides, amides, imides, anhydrides, esters and the like. Specific examples of such derivatives include maleyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate and the like. Of these, unsaturated dicarboxylic acids or acid anhydrides thereof are suitable, and maleic acid, nadic acid or acid anhydrides thereof are particularly preferably used.
[0010]
The modified propylene polymer graft-modified with an unsaturated carboxylic acid or derivative thereof is preferably 0.05 to 15% by weight, more preferably 0.1 to 10% by weight, based on the propylene polymer before modification. Graft-modified with carboxylic acid or its derivative. The modified propylene polymer preferably has a melt flow rate (MFR, 230 ° C.) of 0.1 to 50 g / 10 minutes, more preferably MFR of 0.3 to 30 g / 10 minutes.
[0011]
Acrylic UV-absorbing resin (B)
The acrylic ultraviolet absorbing resin (B) according to the present invention includes (meth) acrylic acid ester (C) having a UV absorbing function such as a benzotriazole group or a benzophenone group having an ultraviolet absorbing function as a copolymerization component and other components. It is a copolymer with (meth) acrylic acid ester (D).
(Meth) acrylic acid ester (C) is a compound represented by the following general formula (1).
CH 2 = CR 1 (COOR 2 ) (1)
(R 1 represents a hydrogen atom or a methyl group, and R 2 represents a hydrocarbon group containing an ultraviolet absorbing group.)
As a specific example of the (meth) acrylic acid ester (C), when the ultraviolet absorbing group is a benzotriazole group, for example, 2- [2′-hydroxy-5 ′-(meth) acryloyloxymethylphenyl] -2H -Benzotriazole, 2- [2'-hydroxy-5 '-(meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(meth) acryloyloxypropylphenyl] -2H -Benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-tert-butyl -3 ′-(meth) acryloyloxyethylphenyl] -2H-benzotriazole and the like.
[0012]
When the ultraviolet absorbing group is a benzophenone group, for example, 2-hydroxy-4- [2- (meth) acryloyloxy] ethoxybenzophenone, 2-hydroxy-4- [2- (meth) acryloyloxy] butoxybenzophenone, 2-hydroxy-4- [2- (meth) acryloyloxy] ethoxy-4 ′-(2-hydroxyethoxy) benzophenone and the like can be mentioned.
(Meth) acrylic acid ester (D) is a compound represented by general formula (2).
CH 2 = CR 3 (COOR 4 ) (2)
(R 3 represents a hydrogen atom or a methyl group, and R 4 is a hydrogen atom, or a hydrocarbon group having 1 to 9 carbon atoms, a hydrocarbon group containing a functional group, or a hydrocarbon group containing a UV-stable group. Is shown.)
Specific examples of (meth) acrylic acid ester (D) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) ) Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acrylo Ruamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4 (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4-cyano -4 (meth) acryloylamino-2,2,6,6-tetramethylpiperidine and the like. 1 type (s) or 2 or more types may be used for this (meth) acrylic acid ester (D).
[0013]
In the acrylic ultraviolet absorbing resin (B) according to the present invention, the proportion of the (meth) acrylic acid ester (C) to which an ultraviolet absorbing group such as a benzotriazole group or a benzophenone group having an ultraviolet absorbing function is bonded is the other (meth). When the acrylic ester (D) is 100 parts by weight, it is in the range of 10 to 150 parts by weight. When the amount of the (meth) acrylic acid ester (C) is less than 10 parts by weight, a sufficient anti-ultraviolet effect may not be obtained when the biaxially stretched polypropylene multilayer film is used. On the other hand, when the amount exceeds 150 parts by weight. There is a possibility that the cohesive strength of the coating film is lowered or the transparency is impaired.
The production method of the acrylic ultraviolet absorbing resin (B) according to the present invention is not particularly limited, and a conventionally known polymerization method can be employed, and examples thereof include emulsion polymerization, solution polymerization, suspension polymerization and the like. .
[0014]
The acrylic ultraviolet absorbing resin (B) according to the present invention may contain one or more polymers other than the acrylic ultraviolet absorbing resin as necessary within the range not inhibiting the action. The polymer other than the acrylic ultraviolet absorbing resin is not particularly limited, and examples thereof include thermoplastic resins and thermosetting resins such as polyvinyl chloride resin, polyester resin, acrylic resin, urethane resin, and silicone resin. It is done.
Moreover, 1 type (s) or 2 or more types of crosslinking agents can also be added to the said acrylic type ultraviolet absorption resin (B). The crosslinking agent is not particularly limited, such as an isocyanate type, and the addition amount can be added as long as the action of the acrylic ultraviolet absorbing resin (B) is not inhibited.
[0015]
The acrylic ultraviolet absorbing resin (B) of the present invention is preferably a dispersion in order to be applied to the surface of the biaxially oriented polypropylene film, and the dispersion medium is preferably water from the viewpoints of cost and work environment. The solid content concentration of these aqueous dispersions is usually 1 to 60% by weight, preferably 5 to 50% by weight. If the solid content concentration of the dispersion is less than 1% by weight, thick coating is required to obtain a constant coating thickness, which may reduce productivity and wettability. On the other hand, those exceeding 60% by weight have high viscosity and may cause uneven coating.
In addition, various additives such as a lubricant, a slip agent, an anti-blocking agent, an antistatic agent, an antifogging agent, a pigment, a dye, an inorganic or an organic filler are added to the aqueous dispersion as necessary. You may add in the range which does not impair.
[0016]
Biaxially stretched polypropylene multilayer film The biaxially stretched polypropylene multilayer film of the present invention comprises an acrylic ultraviolet absorbing resin (B) layer on one side of a biaxially stretched polypropylene film via a modified propylene polymer (A) layer. Are laminated. By passing the modified propylene polymer (A) layer, the acrylic ultraviolet absorbing resin (B) layer can be strongly bonded to the biaxially oriented polypropylene layer. By laminating on the combined (A) layer and then stretching together with the modified propylene polymer (A) layer, a biaxially stretched polypropylene multilayer film having strong adhesive force even under high humidity is obtained.
The thickness of each layer in the biaxially stretched polypropylene multilayer film is variously determined depending on the application, but usually the thickness of the biaxially stretched polypropylene film is 10 to 100 μm, preferably 15 to 60 μm, and the modified propylene polymer (A) layer Is 0.2 to 10 μm, preferably 0.5 to 5 μm, and the acrylic ultraviolet absorbing resin (B) layer is 0.3 to 20 μm, preferably 0.5 to 10 μm, further 0.8 μm. It is in the range of ˜5 μm.
In the biaxially oriented polypropylene multilayer film of the present invention, it is usually desirable that the ultraviolet transmittance at 370 nm is 30% or less, more preferably 20% or less, and still more preferably 10% or less. By setting the ultraviolet transmittance of 370 nm within such a range, it is possible to suppress adverse effects due to ultraviolet rays such as alteration of contents such as food and discoloration of printed matter. If the ultraviolet transmittance at 370 nm exceeds 30%, these functions may not be sufficient.
[0017]
Method for producing biaxially oriented polypropylene multilayer film The method for producing a biaxially oriented polypropylene multilayer film of the present invention is obtained by coextrusion molding of polypropylene and a modified propylene polymer (A) to obtain a sheet, followed by modification. After coating the acrylic ultraviolet absorbing resin (B) on the propylene polymer (A) layer, a method of stretching the laminated sheet, or coextrusion molding of polypropylene and the modified propylene polymer (A) to form a sheet After being obtained, the sheet is stretched in the longitudinal direction, and the acrylic propylene polymer (B) is coated on the modified propylene polymer (A) layer and then stretched in the transverse direction.
Examples of the method of coating the acrylic ultraviolet absorbing resin (B) on the unstretched laminated sheet or the modified propylene polymer (A) after longitudinal stretching include, for example, an air knife coater, a direct gravure coater, a gravure offset, an arc gravure coater, Gravure reverse and jet nozzle type gravure coaters, top feed reverse coaters, bottom feed reverse coaters and reverse feed roll coaters such as nozzle feed reverse coaters, 5-roll coaters, lip coaters, bar coaters, bar reverse coaters, die coaters, etc. Using a known coating machine, the solid content in the acrylic ultraviolet absorbing resin (B) dispersion is 3 to 200 g / m 2 , preferably 5 to 100 g / m 2, and then 50 to Dry at a temperature of 140 ° C Obtained by Rukoto. The surface on which the acrylic ultraviolet absorbing resin (B) dispersion is applied, that is, the modified propylene polymer (A) is subjected to corona treatment or the like in advance in order to improve wettability with the acrylic ultraviolet absorbing resin (B). It may be left.
The stretching temperature and the stretching ratio of the biaxially stretched polypropylene multilayer film are the usual conditions, for example, simultaneous biaxial stretching, the stretching temperature is 150 to 190 ° C., and the stretching ratio is 3 to 10 times in length and width respectively. In the case of sequential biaxial stretching, the longitudinal stretching temperature is 125 to 145 ° C., the stretching ratio is 4.5 to 6 times, and the lateral width after applying and drying the acrylic ultraviolet absorbing resin (B). What is necessary is just to extend | stretch by making a extending | stretching temperature into 150-190 degreeC and a draw ratio in the range of 9-11 times.
[0018]
【The invention's effect】
In the biaxially stretched polypropylene multilayer film of the present invention, the acrylic ultraviolet absorbing resin layer is firmly bonded to the biaxially stretched polypropylene layer. Furthermore, the biaxially stretched polypropylene multilayer film obtained by the method of the present invention maintains the adhesive force between the biaxially stretched polypropylene layer and the acrylic ultraviolet absorbing resin layer even under high humidity. Accordingly, the biaxially stretched polypropylene multilayer film of the present invention has ultraviolet ray prevention properties in addition to the characteristics inherent to the biaxially stretched polypropylene film, such as transparency, mechanical strength, and rigidity. It can be suitably used as a packaging material for foods such as fats and oils such as snacks and confectionery, cosmetics, pharmaceuticals, foods that dislike the fading of pigments, and clothing. In addition, by stacking a layer having a gas barrier property or a water vapor barrier property, for example, an ethylene / vinyl alcohol copolymer layer, a polyvinyl alcohol layer, an aluminum oxide vapor deposition layer, a silicon oxide vapor deposition layer, a conventional aluminum foil, etc. Therefore, it can be used as a packaging material capable of recognizing the contents even for packaging requiring light shielding. Furthermore, for industrial materials, it can be used as a protective film to suppress discoloration of printed matter and deterioration of the substrate by laminating on the surface of posters, menu tables, books and binder covers, bulletins, guide plates and the like.
[0019]
【Example】
EXAMPLES Next, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
[0020]
Example 1
Melting point: 162 ° C., MFR: 2 g / 10 min of polypropylene as a base material layer, obtained by coextrusion of modified polypropylene graft-modified with maleic anhydride on one side of melting point: 165 ° C., MFR: 3 g / 10 min After the multilayer film has been stretched 5 times in the longitudinal direction, UV absorption containing 0.1 part by weight of an acrylic UV absorbing resin and an anti-blocking agent (polymethyl methacrylate particles having an average particle size of 1.2 μm) on the surface of the modified polypropylene layer An acrylic polymer emulsion (product name: Cybinol X-501-510E-1 concentration: 40% by weight) coated with 20 cc gravure roll and dried. Next, the film was stretched 10 times in the transverse direction in a tenter in which hot air at 160 ° C. was circulated, and then fixed with hot air at 150 ° C. for 5 seconds to obtain a biaxially oriented polypropylene multilayer film. The thickness of each layer of the obtained multilayer film was 20 μm for the polypropylene film base layer, 1 μm for the modified polypropylene layer, and 0.8 μm for the acrylic ultraviolet absorbing resin layer.
The obtained biaxially stretched polypropylene multilayer film was evaluated by the following method.
[0021]
(1) Adhesion test of acrylic UV-absorbing resin layer (peel strength)
On the corona-treated surface of a linear low density polyethylene film (product name: TUX FCD # 50, manufactured by Tosero Co., Ltd.) having a thickness of 50 μm, an adhesive for polyurethane-based dry lamination (product name: Takelac A310: Takenate A3 manufactured by Mitsui Takeda) The solution was mixed with 12: 1 and diluted with ethyl acetate to apply 2.5 g / m 2, and then laminated with an acrylic ultraviolet absorbing resin of a biaxially oriented polypropylene multilayer film. After the laminated film was aged at 40 ° C. for 24 hours, the biaxially stretched polypropylene multilayer film and the polyethylene film were peeled off at a peeling speed of 300 mm / min, and the strength was measured. The laminated film aged at 40 ° C. for 24 hours was left in an incubator (40 ° C., 90% RH) for 24 hours, and the peel strength was similarly measured at a peel rate of 300 mm / min.
(2) Ultraviolet-absorbing A spectrophotometer Ubest-35 type manufactured by JASCO Corporation was used to measure the absorptivity at a wavelength of 320 nm of one biaxially oriented polypropylene multilayer film.
Table 1 shows the measurement results of the biaxially stretched polypropylene multilayer film.
[0022]
Comparative Example 1
A biaxially stretched polypropylene laminated film was obtained in the same manner as in Example 1 except that polypropylene having a melting point of 162 ° C. and MFR of 2 g / 10 min was used instead of the modified polypropylene used in Example 1. The obtained laminated film was evaluated in the same manner as in Example 1. The measurement results are shown in Table 1.
[0023]
Comparative Example 2
Melting point: 162 ° C., MFR: 2 g / 10 min of polypropylene as an intermediate layer, co-extruded multilayer film in which modified polypropylene grafted with maleic anhydride, melting point: 165 ° C., MFR: 3 g / 10 min, is laminated on one side Was stretched 5 times in the longitudinal direction, then stretched 10 times in the transverse direction in a tenter circulated with hot air at 160 ° C., heat-fixed at 150 ° C. for 5 seconds, and further subjected to corona treatment on the modified polypropylene laminate surface. And a biaxially stretched polypropylene laminated film having a wetting tension of 38 dynes was obtained. The corona-treated modified polypropylene layer was coated with 4 cc of the UV-absorbing acrylic polymer emulsion (concentration: 20% by weight) used in Example 1 and dried to obtain a biaxially stretched polypropylene laminated film. The thickness of each layer of the obtained laminated film was 20 μm for the polypropylene layer, 1 μm for the modified polypropylene layer, and 0.8 μm for the acrylic ultraviolet absorbing resin layer. The obtained laminated film was evaluated in the same manner as in Example 1. The measurement results are shown in Table 1.
[0024]
[Table 1]
As is clear from Table 1, the biaxially stretched polypropylene multilayer film obtained in Example 1 had a larger initial peel strength than the biaxially stretched polypropylene multilayer film obtained in Comparative Example 1, and was treated under high humidity. There is no decrease in the peel strength. Although the biaxially stretched polypropylene multilayer film obtained in Comparative Example 2 has excellent initial peel strength, the peel strength after treatment under high humidity decreases. Therefore, by providing the modified propylene polymer layer on the biaxially stretched polypropylene layer, the adhesive strength with the acrylic ultraviolet absorbing resin layer is improved. However, after the biaxially stretched polypropylene layer and the modified propylene polymer layer are longitudinally stretched, A biaxially stretched polypropylene multilayer film excellent in high humidity resistance can be obtained by covering the modified propylene polymer layer with an acrylic ultraviolet absorbing resin layer and stretching it laterally.
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