JP2013252645A - Biaxially-stretched multilayered polypropylene film - Google Patents
Biaxially-stretched multilayered polypropylene film Download PDFInfo
- Publication number
- JP2013252645A JP2013252645A JP2012129121A JP2012129121A JP2013252645A JP 2013252645 A JP2013252645 A JP 2013252645A JP 2012129121 A JP2012129121 A JP 2012129121A JP 2012129121 A JP2012129121 A JP 2012129121A JP 2013252645 A JP2013252645 A JP 2013252645A
- Authority
- JP
- Japan
- Prior art keywords
- propylene polymer
- layer
- biaxially stretched
- polypropylene film
- surface layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 193
- -1 polypropylene Polymers 0.000 title claims abstract description 82
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 68
- 239000010410 layer Substances 0.000 claims abstract description 95
- 239000000203 mixture Substances 0.000 claims abstract description 76
- 239000002344 surface layer Substances 0.000 claims abstract description 68
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 55
- 239000000843 powder Substances 0.000 claims abstract description 12
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 10
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 63
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- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 31
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 30
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 29
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 24
- 239000002245 particle Substances 0.000 claims description 19
- 239000011247 coating layer Substances 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 7
- 230000009477 glass transition Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 17
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- 239000011347 resin Substances 0.000 abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
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- 239000001301 oxygen Substances 0.000 abstract description 9
- 230000000903 blocking effect Effects 0.000 abstract description 8
- 230000004888 barrier function Effects 0.000 abstract description 6
- 239000005022 packaging material Substances 0.000 abstract description 6
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- 239000011127 biaxially oriented polypropylene Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 150000004665 fatty acids Chemical class 0.000 description 9
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- 239000002667 nucleating agent Substances 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
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- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 150000001565 benzotriazoles Chemical class 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
- 239000004305 biphenyl Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
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- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000005003 food packaging material Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- VXZBFBRLRNDJCS-UHFFFAOYSA-N heptacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O VXZBFBRLRNDJCS-UHFFFAOYSA-N 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- ISYWECDDZWTKFF-UHFFFAOYSA-N nonadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCCC(O)=O ISYWECDDZWTKFF-UHFFFAOYSA-N 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 2
- 239000005026 oriented polypropylene Substances 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
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- 150000005846 sugar alcohols Polymers 0.000 description 2
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- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- CSUUDNFYSFENAE-UHFFFAOYSA-N (2-methoxyphenyl)-phenylmethanone Chemical compound COC1=CC=CC=C1C(=O)C1=CC=CC=C1 CSUUDNFYSFENAE-UHFFFAOYSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
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- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FARYTWBWLZAXNK-WAYWQWQTSA-N ethyl (z)-3-(methylamino)but-2-enoate Chemical compound CCOC(=O)\C=C(\C)NC FARYTWBWLZAXNK-WAYWQWQTSA-N 0.000 description 1
- IAJNXBNRYMEYAZ-UHFFFAOYSA-N ethyl 2-cyano-3,3-diphenylprop-2-enoate Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC)C1=CC=CC=C1 IAJNXBNRYMEYAZ-UHFFFAOYSA-N 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 235000013305 food Nutrition 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
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002314 glycerols Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- LDHQCZJRKDOVOX-IHWYPQMZSA-N isocrotonic acid Chemical compound C\C=C/C(O)=O LDHQCZJRKDOVOX-IHWYPQMZSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 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
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000011888 snacks Nutrition 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 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
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Abstract
Description
本発明は、隠蔽性、水蒸気及び酸素等に対するバリア性を有し、表面光沢、表面平滑性、ラミネート適性、耐ブロッキング性などに優れる包装材料に好適な二軸延伸多層ポリプロピレンフィルムに関する。 The present invention relates to a biaxially stretched multilayer polypropylene film suitable for a packaging material having concealing properties, barrier properties against water vapor, oxygen and the like, and excellent in surface gloss, surface smoothness, laminate suitability, blocking resistance, and the like.
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、剛性等の特性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。また、ＯＰＰフィルムの隠蔽性を改良するとともに、表面光沢性を付与する方法として、芯材となるポリプロピレンにナイロン等の有機質材料、あるいはガラスビード等の無機材料等の非相溶性材料を添加し、表面層は無添加のポリプロピレン層とした二軸延伸フィルム（特許文献１）が提案されている。 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 properties such as transparency, mechanical strength, and rigidity. Moreover, while improving the concealability of the OPP film, as a method of imparting surface glossiness, an incompatible material such as an organic material such as nylon or an inorganic material such as glass beads is added to polypropylene as a core material, A biaxially stretched film (Patent Document 1) in which the surface layer is an additive-free polypropylene layer has been proposed.
一方、隠蔽性を改良した二軸延伸多層ポリプロピレンフィルムとして、二軸延伸フィルムの基材層に炭酸カルシウムと酸化チタンを併用した二軸延伸多層フィルム（特許文献２）が提案されている。 On the other hand, as a biaxially stretched multilayer polypropylene film with improved concealability, a biaxially stretched multilayer film in which calcium carbonate and titanium oxide are used in combination on the base layer of the biaxially stretched film has been proposed (Patent Document 2).
特許文献２には、他の物質との接着性を増すために、延伸フィルムの表面をイミン、ウレタン等の接着剤でアンカー処理、あるいは、無水マレイン酸変性ポリオレフィンを積層することが提案されているが、単にウレタン等の接着剤をコーティングしても、耐ブロッキング性は改良されず、また、接着性も不十分である。 Patent Document 2 proposes anchoring the surface of a stretched film with an adhesive such as imine or urethane, or laminating maleic anhydride-modified polyolefin in order to increase adhesion with other substances. However, even if an adhesive such as urethane is simply coated, the blocking resistance is not improved, and the adhesiveness is insufficient.
本発明は、隠蔽性、水蒸気及び酸素等に対するバリア性を有し、表面光沢、表面平滑性、ラミネート適性、耐ブロッキング性などに優れる包装材料に好適な二軸延伸多層ポリプロピレンフィルムを開発することを目的とする。 The present invention develops a biaxially stretched multilayer polypropylene film suitable for a packaging material having concealability, barrier properties against water vapor, oxygen, etc., and having excellent surface gloss, surface smoothness, laminate suitability, blocking resistance, etc. Objective.
本発明は、プロピレン重合体（ａ１）に無機化合物粉末（ａ２）を添加してなるプロピレン重合体組成物（Ａ）から得られる二軸延伸フィルム基材層の片面に、変性プロピレン重合体（ｂ１）を含むプロピレン重合体（Ｂ）からなる表面層、及び他の片面にプロピレン重合体（Ｃ）からなる裏面層が積層されてなり、表面層上に、ポリウレタン系樹脂（Ｄ）からなる被覆層が形成されてなることを特徴とする二軸延伸多層ポリプロピレンフィルムに係る。 The present invention provides a modified propylene polymer (b1) on one side of a biaxially stretched film substrate layer obtained from a propylene polymer composition (A) obtained by adding an inorganic compound powder (a2) to a propylene polymer (a1). ) And a back layer made of a propylene polymer (C) on the other side, and a coating layer made of a polyurethane resin (D) on the surface layer. The biaxially stretched multilayer polypropylene film is characterized in that is formed.
本発明の二軸延伸多層ポリプロピレンフィルムは、隠蔽性、酸素等に対するバリア性を有し、表面光沢、表面平滑性、ラミネート適性、耐ブロッキング性などに優れるので、例えば、スナック、アイス、ビスケットなどの食品包装用を始め、あらゆる包装用材料に好適に使用できる。 The biaxially stretched multilayer polypropylene film of the present invention has a concealing property, a barrier property against oxygen, etc., and is excellent in surface gloss, surface smoothness, suitability for lamination, blocking resistance, etc., for example, snacks, ice, biscuits, etc. It can be suitably used for all packaging materials including food packaging.
＜プロピレン系重合体（ａ１）＞
本発明の二軸延伸多層ポリプロピレンフィルムの二軸延伸フィルム基材層を形成するプロピレン重合体組成物（Ａ）を構成するプロピレン系重合体（ａ１）は、一般にポリプロピレンの名称で製造・販売されているポリオレフィン樹脂であり、通常、密度が０．８９０ないし０．９３０ｇ／ｃｍ3、ＭＦＲ（ＡＳＴＭ Ｄ１２３８ 荷重２１６０ｇ，温度２３０℃）が０．５ないし６０ｇ／１０分、好ましくは０．５ないし１０ｇ／１０分、より好ましくは１ないし５ｇ／１０分のプロピレンの単独重合体、若しくはプロピレンと、他の少量、例えば、５モル％以下のα−オレフィン、例えば、エチレン、１−ブテン、１−ヘキセン、４−メチル・１−ペンテン、１−オクテン等とのランダム共重合体である。
<Propylene-based polymer (a1)>
The propylene polymer (a1) constituting the propylene polymer composition (A) forming the biaxially stretched film base material layer of the biaxially stretched multilayer polypropylene film of the present invention is generally produced and sold under the name of polypropylene. A polyolefin resin having a density of 0.890 to 0.930 g / cm 3 and an MFR (ASTM D1238 load of 2160 g, temperature of 230 ° C.) of 0.5 to 60 g / 10 minutes, preferably 0.5 to 10 g / A homopolymer of propylene for 10 minutes, more preferably 1 to 5 g / 10 min, or propylene and other small amounts, for example 5 mol% or less of α-olefins such as ethylene, 1-butene, 1-hexene, Random copolymers with 4-methyl / 1-pentene, 1-octene and the like.
これらプロピレン系重合体（ａ１）は、１種あるいは２種以上の組成物、例えば、分子量の異なるプロピレンの単独重合体とプロピレン・α−オレフィンランダム共重合体との組成物であってもよい。 These propylene polymers (a1) may be one or more compositions, for example, a composition of a propylene homopolymer and a propylene / α-olefin random copolymer having different molecular weights.
また、プロピレン系重合体（ａ１）として、プロピレン単独重合体、若しくは１モル％以下のランダム共重合体でアイソタクテシティの高い重合体が高剛性を有する二軸延伸多層ポリプロピレンフィルムが得られる。
＜無機化合物粉末（ａ２）＞
本発明に係る無機化合物粉末（ａ２）とは、炭酸カルシウム、クレー（カオリン）、焼成クレー、タルク、シリカ、ゼオライト、硫酸バリウム、硫酸アルミニウム、酸化チタン等の粉末で、通常、平均粒径が５μｍ以下、好ましくは０．１ないし１．５μｍの範囲のものである。これら無機化合物粉末の中でも、炭酸カルシウム及び酸化チタンが、むらのない白色度に優れた二軸延伸多層ポリプロピレンフィルムが得られる点で好ましい。
Further, as the propylene polymer (a1), a biaxially stretched multilayer polypropylene film in which a propylene homopolymer or a random copolymer of 1 mol% or less and a polymer having high isotacticity has high rigidity is obtained.
<Inorganic compound powder (a2)>
The inorganic compound powder (a2) according to the present invention is a powder of calcium carbonate, clay (kaolin), calcined clay, talc, silica, zeolite, barium sulfate, aluminum sulfate, titanium oxide or the like, and usually has an average particle size of 5 μm. The thickness is preferably in the range of 0.1 to 1.5 μm. Among these inorganic compound powders, calcium carbonate and titanium oxide are preferable in that a biaxially stretched multilayer polypropylene film excellent in uneven whiteness can be obtained.
＜炭酸カルシウム＞
本発明の二軸延伸多層ポリプロピレンフィルムの二軸延伸フィルム基材層を形成するプロピレン重合体組成物（Ａ）を構成する炭酸カルシウムは、平均粒子径が１〜５μｍ、好ましくは１．５〜４μｍの範囲にある。
<Calcium carbonate>
The calcium carbonate constituting the propylene polymer composition (A) forming the biaxially stretched film base layer of the biaxially stretched multilayer polypropylene film of the present invention has an average particle diameter of 1 to 5 μm, preferably 1.5 to 4 μm. It is in the range.
本発明に係る炭酸カルシウムは、好ましくは、その粒子表面が高級脂肪酸、好ましくは炭素原子数１０〜２８の高級脂肪酸で表面処理された炭酸カルシウムである。かかる高級脂肪酸でその粒子表面が処理されていることにより、炭酸カルシウムの２次凝集による異物、フィッシュアイ等の発生を防止することができ、良好な外観を呈する二軸延伸多層ポリプロピレンフィルムが得られる。 The calcium carbonate according to the present invention is preferably calcium carbonate whose surface is treated with a higher fatty acid, preferably a higher fatty acid having 10 to 28 carbon atoms. By treating the particle surface with such a higher fatty acid, it is possible to prevent the occurrence of foreign matters, fish eyes and the like due to secondary aggregation of calcium carbonate, and a biaxially stretched multilayer polypropylene film having a good appearance can be obtained. .
高級脂肪酸としては、具体的には、デカン酸、ウンデカン酸、ラウリン酸、トリデシル酸、ミリスチン酸、ペンタデシル酸、パルミチン酸、ヘプタデシル酸、ステアリン酸、ノナデカン酸、アラキン酸、ベヘン酸、リグノセリン酸、セロチン酸、ヘプタコサン酸等の飽和高級脂肪酸［ＣＨ3（ＣＨ2）nＣＯＯＨ、ｎ＝８〜２６］；オレイン酸（cis)、エライジン酸（trans)、セトレイン酸、エルカ酸（cis)、ブラシジン酸（trans)、リノール酸、リノレン酸、アラキドン酸等の不飽和高級脂肪酸などが挙げられる。これら中でも、飽和高級脂肪酸、特にステアリン酸が好ましい。 Specific examples of the higher fatty acid include decanoic acid, undecanoic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachidic acid, behenic acid, lignoceric acid, and serothin. Saturated higher fatty acids [CH 3 (CH 2 ) nCOOH, n = 8 to 26] such as acid and heptacosanoic acid; oleic acid (cis), elaidic acid (trans), cetreic acid, erucic acid (cis), brassic acid (trans ), Unsaturated higher fatty acids such as linoleic acid, linolenic acid and arachidonic acid. Of these, saturated higher fatty acids, particularly stearic acid, are preferred.
本発明に係る炭酸カルシウムは、好ましくは、最大粒子径が、１０μｍ以下、より好ましくは９μｍ以下である。
なお、粒子径は、超遠心式自動粒度分布測定装置（型式 ＣＡＰＡ−７００、堀場製作所製）を用い遠心沈降による光透過測定方式にて測定した。
The calcium carbonate according to the present invention preferably has a maximum particle size of 10 μm or less, more preferably 9 μm or less.
The particle size was measured by a light transmission measurement method by centrifugal sedimentation using an ultracentrifugal automatic particle size distribution analyzer (model CAPA-700, manufactured by Horiba, Ltd.).
又、本発明に係る炭酸カルシウムは、好ましくは粒径が５μｍ以下の炭酸カルシウム粒子が、炭酸カルシウム全体の８０質量％以上、好ましくは８５質量％以上占める粒度分布を有する。このような粒度分布と平均粒径とを有する炭酸カルシウムを用いると、炭酸カルシウム粒子によるボイドの大きさが均一となるため、むらのない白色度が優れるフィルムが得られる。 The calcium carbonate according to the present invention preferably has a particle size distribution in which calcium carbonate particles having a particle size of 5 μm or less occupy 80% by mass or more, preferably 85% by mass or more of the total calcium carbonate. When calcium carbonate having such a particle size distribution and average particle size is used, the size of voids due to the calcium carbonate particles becomes uniform, so that a film with excellent whiteness without unevenness can be obtained.
本発明に係る炭酸カルシウムは、均一でかつ白色度に優れたフィルムを得るために、炭酸カルシウムの水分が、０．５質量％以下であることがより好ましい。かかる水分は、ＪＩＳ Ｋ ５１０１に準じて測定した。さらには、白色度は、９０％以上の炭酸カルシウムがより好ましい。 In order that the calcium carbonate which concerns on this invention may obtain the film which was uniform and excellent in whiteness, it is more preferable that the water | moisture content of calcium carbonate is 0.5 mass% or less. Such moisture was measured according to JIS K 5101. Furthermore, the whiteness is more preferably 90% or more of calcium carbonate.
＜酸化チタン＞
本発明の二軸延伸多層ポリプロピレンフィルムの二軸延伸フィルム基材層を形成するプロピレン重合体組成物（Ａ）を構成する酸化チタンは、平均粒子径が０．１〜０．５μｍ、好ましくは０．２〜０．３μｍの範囲にある。酸化チタンは、チタンホワイトとも呼ばれており、ルチル型とアナターゼ型があるが、ルチル型が、隠蔽力が大きいので好ましい。又、本発明の係る酸化チタンは、その表面が、アルミナ処理されていることが好ましい。さらには、白色度が９５％以上のものが好ましい。酸化チタンの表面を処理したものを使用することにより、得られる二軸延伸多層ポリプロピレンフィルムの外観が改良される。
<Titanium oxide>
The titanium oxide constituting the propylene polymer composition (A) forming the biaxially stretched film base material layer of the biaxially stretched multilayer polypropylene film of the present invention has an average particle size of 0.1 to 0.5 μm, preferably 0. In the range of 2 to 0.3 μm. Titanium oxide is also called titanium white, and there are a rutile type and an anatase type, but the rutile type is preferable because of its high hiding power. The surface of the titanium oxide according to the present invention is preferably treated with alumina. Furthermore, the thing whose whiteness is 95% or more is preferable. The appearance of the obtained biaxially stretched multilayer polypropylene film is improved by using a material obtained by treating the surface of titanium oxide.
なお、酸化チタンの粒子径は、光散乱法により測定した。
＜プロピレン重合体組成物（Ａ）＞
本発明の二軸延伸多層ポリプロピレンフィルムの二軸延伸フィルム基材層を形成するプロピレン重合体組成物（Ａ）は、前記プロピレン重合体（ａ１）に前記無機化合物粉末（ａ２）を添加してなる組成物である。
The particle diameter of titanium oxide was measured by a light scattering method.
<Propylene polymer composition (A)>
The propylene polymer composition (A) for forming the biaxially stretched film base layer of the biaxially stretched multilayer polypropylene film of the present invention is obtained by adding the inorganic compound powder (a2) to the propylene polymer (a1). It is a composition.
本発明に係るプロピレン重合体組成物（Ａ）は、好ましくは、プロピレン重合体（ａ１）を７０〜９５質量％、より好ましくは７０〜９０質量％、炭酸カルシウムを３〜１５質量％、より好ましくは５〜１５質量％及び酸化チタンを０．５〜３．０質量％、より好ましくは０．８〜２．７質量％からなる無機化合物粉末（ａ２）を含む組成物〔（ａ１）＋（ａ２）＝１００質量％〕である。 In the propylene polymer composition (A) according to the present invention, the propylene polymer (a1) is preferably 70 to 95% by mass, more preferably 70 to 90% by mass, and calcium carbonate 3 to 15% by mass, more preferably. Is a composition containing an inorganic compound powder (a2) consisting of 5 to 15% by mass and titanium oxide 0.5 to 3.0% by mass, more preferably 0.8 to 2.7% by mass [(a1) + ( a2) = 100 mass%].
炭酸カルシウム（ａ２）の量が３質量％未満では、得られる二軸延伸多層ポリプロピレンフィルムの隠蔽性が劣る虞があり、一方、１５質量％を越えると、得られる二軸延伸多層ポリプロピレンフィルムの外観が損なわれる虞がある。 If the amount of calcium carbonate (a2) is less than 3% by mass, the concealability of the resulting biaxially stretched multilayer polypropylene film may be inferior. On the other hand, if it exceeds 15% by mass, the resulting biaxially stretched multilayer polypropylene film has an appearance. May be damaged.
酸化チタン（ａ３）の量が０．５質量％未満では、得られる二軸延伸多層ポリプロピレンフィルムの隠蔽性が劣る虞があり、一方、３．０質量％を越えると、得られる二軸延伸多層ポリプロピレンフィルムの外観が損なわれる虞がある。 When the amount of titanium oxide (a3) is less than 0.5% by mass, the concealability of the resulting biaxially stretched multilayer polypropylene film may be inferior. There exists a possibility that the external appearance of a polypropylene film may be impaired.
本発明に係るプロピレン重合体組成物（Ａ）、あるいは、本発明に係るプロピレン重合体（ａ１）には、必要に応じて、耐熱安定剤、耐候安定剤、紫外線吸収剤、滑剤、スリップ剤、核剤、ブロッキング防止剤、帯電防止剤、防曇剤、顔料、染料等の通常ポリオレフィンに用いる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おいてもよい。 If necessary, the propylene polymer composition (A) according to the present invention or the propylene polymer (a1) according to the present invention includes a heat stabilizer, a weather stabilizer, an ultraviolet absorber, a lubricant, a slip agent, Various additives such as a nucleating agent, an antiblocking agent, an antistatic agent, an antifogging agent, a pigment, and a dye that are usually used for polyolefins may be added within a range not impairing the object of the present invention.
耐熱安定剤（酸化防止剤）としては、例えば、３，５―ジーｔ−ブチルー４−ヒドロキシトルエン、テトラキス［メチレン（３，５―ジーｔ―ブチルー４―ヒドロキシ）ヒドロシンナメート］メタン、ｎ−オクタデシルー３−（４'―ヒドロキシー３，５−ジーｔ―ブチルフェニル）プロピオネート、２，２'−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）等のフェノール系酸化防止剤、２−ヒドロキシ−４−メトキシベンゾフェノン、２−ヒドロキシ−４−オクトキシベンゾフェノン、２，４−ジヒドロキシベンゾフェノン等のベンゾフェノン系酸化防止剤、２（２'−ヒドロキシ−５−メチルフェニル）ベンゾトリアゾール、置換ベンゾトリアゾール等のベンゾトリアゾール系酸化防止剤、２−エチルヘキシル−２−シアノ−３，３−ジフェニルアクリレート、エチル−２−シアノ−３，３−ジフェニルアクリレート、フェニルサルチレート、４−ｔ−ブチルフェニルサリチレート等が挙げられる。 As the heat stabilizer (antioxidant), for example, 3,5-di-t-butyl-4-hydroxytoluene, tetrakis [methylene (3,5-di-t-butyl-4-hydroxy) hydrocinnamate] methane, n- Phenolic antioxidants such as octadecyl-3- (4′-hydroxy-3,5-di-t-butylphenyl) propionate, 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2-hydroxy-4 Benzophenone antioxidants such as 2-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2,4-dihydroxybenzophenone, benzotriazoles such as 2 (2′-hydroxy-5-methylphenyl) benzotriazole, substituted benzotriazole -Based antioxidant, 2-ethylhexyl-2-cyano-3 3-diphenyl acrylate, ethyl-2-cyano-3,3-diphenyl acrylate, phenyl salicylate, and a 4-t-butylphenyl salicylate and the like.
帯電防止剤としては、例えば、アルキルアミンおよびその誘導体、高級アルコール、高級脂肪酸のグリセリンエステル類、ピリジン誘導体、硫酸化油、石鹸類、オレフィンの硫酸エステル塩類、アルキル硫酸エステル類、脂肪酸エチルスルフォン酸塩、アルキルスルフォン酸塩、アルキルナフタレンスルフォン酸塩、アルキルベンゼンスルフォン酸塩、ナフタレンスルフォン酸塩、琥珀酸エステルスルフォン酸塩、リン酸エステル塩、多価アルコールの部分的脂肪酸エステル、脂肪アルコールのエチレンオキサイド付加物、脂肪酸のエチレンオキサイド付加物、脂肪アミノまたは脂肪酸アミドのエチレンオキサイド付加物、アルキルフェノールのエチレンオキサイド付加物、アルキルナフトールのエチレンオキサイド付加物、多価アルコールの部分的脂肪酸エステルのエチレンオキサイド付加物、ポリエチレングリコール等が挙げられる。 Antistatic agents include, for example, alkylamines and derivatives thereof, higher alcohols, glycerol esters of higher fatty acids, pyridine derivatives, sulfated oils, soaps, sulfates of olefins, alkyl sulfates, fatty acid ethyl sulfonates , Alkyl sulfonate, alkyl naphthalene sulfonate, alkyl benzene sulfonate, naphthalene sulfonate, oxalate sulfonate, phosphate ester, partial fatty acid ester of polyhydric alcohol, ethylene oxide adduct of fatty alcohol , Fatty acid ethylene oxide adduct, fatty amino or fatty acid amide ethylene oxide adduct, alkylphenol ethylene oxide adduct, alkyl naphthol ethylene oxide adduct, polyhydric alcohol Ethylene oxide adducts of partial fatty acid esters, polyethylene glycol, and the like.
滑剤としては、例えば、ステアリン酸、ステアリン酸アミド、オレイン酸アミド、高級アルコール、流動パラフィン等が挙げられる。
紫外線吸収剤としては、例えば、エチレン−２−シアノ−３，３'−ジフェニルアクリレート、２−（２'−ヒドロキシ−５'−メチルフェニル）ベンゾトリアゾール、２−（２'−ヒドロキシ−３'−ｔ−ブチル−５'−メチルフェニル）５−クロロベンゾトリアゾール、２−ヒドロキシ−４−メトキシベンゾフェノン、２、２'−ジヒドロキシ−４−メトキシベンゾフェノン、２−ヒドロキシ−４オクトキシベンゾフェノン等が挙げられる。
Examples of the lubricant include stearic acid, stearic acid amide, oleic acid amide, higher alcohol, liquid paraffin, and the like.
Examples of the ultraviolet absorber include ethylene-2-cyano-3,3′-diphenyl acrylate, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3′-). t-butyl-5'-methylphenyl) 5-chlorobenzotriazole, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4octoxybenzophenone and the like.
＜プロピレン重合体（Ｂ）＞
本発明の二軸延伸多層ポリプロピレンフィルムの表面層を形成するプロピレン重合体（Ｂ）は、プロピレンの単独重合体、若しくはプロピレンと、他の少量、例えば、５モル％以下のα−オレフィン、例えば、エチレン、１−ブテン、１−ヘキセン、４−メチル・１−ペンテン、１−オクテン等とのランダム共重合体である。ランダム共重合体は、プロピレンと二種以上のα‐オレフィンからなる三元ランダム共重合体であってもよい。
<Propylene polymer (B)>
The propylene polymer (B) that forms the surface layer of the biaxially stretched multilayer polypropylene film of the present invention is a propylene homopolymer or propylene and another small amount, for example, 5 mol% or less α-olefin, for example, Random copolymers with ethylene, 1-butene, 1-hexene, 4-methyl / 1-pentene, 1-octene and the like. The random copolymer may be a ternary random copolymer composed of propylene and two or more α-olefins.
本発明に係るプロピレン重合体（Ｂ）は、通常、ＭＦＲ（ＡＳＴＭ Ｄ１２３８ 荷重２１６０ｇ，温度２３０℃）が０．５ないし６０ｇ／１０分、好ましくは０．５ないし１０ｇ／１０分、より好ましくは１ないし５ｇ／１０分の範囲にある。 The propylene polymer (B) according to the present invention usually has an MFR (ASTM D1238 load 2160 g, temperature 230 ° C.) of 0.5 to 60 g / 10 minutes, preferably 0.5 to 10 g / 10 minutes, more preferably 1 Or in the range of 5 g / 10 min.
本発明に係るプロピレン重合体（Ｂ）として、プロピレン単独重合体とプロピレン・α‐オレフィンランダム共重合体との組成物を用いた場合は、接着性に優れる二軸延伸多層ポリプロピレンフィルムとなる。 When a composition of a propylene homopolymer and a propylene / α-olefin random copolymer is used as the propylene polymer (B) according to the present invention, a biaxially stretched multilayer polypropylene film having excellent adhesiveness is obtained.
本発明に係るプロピレン重合体（Ｂ）として、プロピレン・α‐オレフィンランダム共重合体を用いる場合は、プロピレン・α‐オレフィンランダム共重合体は、通常、融点が１００〜１５０℃、好ましくは１２０〜１４５℃の範囲にある。 When a propylene / α-olefin random copolymer is used as the propylene polymer (B) according to the present invention, the propylene / α-olefin random copolymer usually has a melting point of 100 to 150 ° C., preferably 120 to It is in the range of 145 ° C.
本発明に係るプロピレン重合体（Ｂ）は、下記変性プロピレン重合体（ｂ１）を含む。
また、本発明に係るプロピレン重合体（Ｂ）は、全てが下記変性プロピレン重合体（ｂ１）であってもよいし、下記変性プロピレン重合体（ｂ１）と未変性のプロピレン重合体との組成物であってもよい。
The propylene polymer (B) according to the present invention includes the following modified propylene polymer (b1).
Further, the propylene polymer (B) according to the present invention may all be the following modified propylene polymer (b1), or a composition of the following modified propylene polymer (b1) and an unmodified propylene polymer. It may be.
プロピレン重合体（Ｂ）として、下記変性プロピレン重合体（ｂ１）と未変性のプロピレン重合体との組成物を用いる場合は、変性プロピレン重合体（ｂ１）がプロピレン単独重合体を変性したものと未変性のプロピレン・α‐オレフィンランダム共重合体との組成物、あるいは、プロピレン・α‐オレフィンランダム共重合体を変性した変性プロピレン重合体（ｂ１）と未変性のプロピレン単独重合体との組成物であってもよい。 When the composition of the following modified propylene polymer (b1) and an unmodified propylene polymer is used as the propylene polymer (B), the modified propylene polymer (b1) is a modified propylene homopolymer and an unmodified propylene polymer (B1). A composition of a modified propylene / α-olefin random copolymer, or a composition of a modified propylene polymer (b1) obtained by modifying a propylene / α-olefin random copolymer and an unmodified propylene homopolymer. There may be.
本発明に係るプロピレン重合体（Ｂ）として、プロピレン単独重合体とプロピレン・α−オレフィンランダム共重合体の組成物を用いる場合は、その量比は特に限定はされないが、通常、プロピレン単独重合体とプロピレン・α−オレフィンランダム共重合体の合計量１００質量％に対して、プロピレン単独重合体を２０〜８０質量％、好ましくは２５〜７５質量％含む。その場合は、プロピレン単独重合体およびプロピレン・α−オレフィンランダム共重合体の何れかが変性プロピレン重合体であればよいし、また、何れも変性プロピレン重合体であってもよい。 When the composition of the propylene homopolymer and the propylene / α-olefin random copolymer is used as the propylene polymer (B) according to the present invention, the amount ratio is not particularly limited, but usually the propylene homopolymer The propylene homopolymer is contained in an amount of 20 to 80% by mass, preferably 25 to 75% by mass, based on 100% by mass of the total amount of propylene / α-olefin random copolymer. In that case, either the propylene homopolymer or the propylene / α-olefin random copolymer may be a modified propylene polymer, and any of them may be a modified propylene polymer.
本発明に係るプロピレン重合体（Ｂ）には、上記プロピレン重合体組成物（Ａ）と同様に、必要に応じて、耐熱安定剤、耐候安定剤、紫外線吸収剤、滑剤、スリップ剤、核剤、帯電防止剤、防曇剤、顔料、染料等の通常ポリオレフィンに用いる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おいてもよい。 In the propylene polymer (B) according to the present invention, a heat-resistant stabilizer, a weather-resistant stabilizer, an ultraviolet absorber, a lubricant, a slip agent, and a nucleating agent are added to the propylene polymer composition (A) as necessary. Various additives usually used in polyolefins such as antistatic agents, antifogging agents, pigments and dyes may be added within the range not impairing the object of the present invention.
＜変性プロピレン重合体（ｂ１）＞
本発明の二軸延伸多層ポリプロピレンフィルムの表面層を形成するプロピレン重合体（Ｂ）に含まれる変性プロピレン重合体（ｂ１）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、ポリウレタン系樹脂（Ｄ）からなる被覆層との接着性の改善効果に優れるので好ましい。
<Modified propylene polymer (b1)>
The modified propylene polymer (b1) contained in the propylene polymer (B) forming the surface layer of the biaxially stretched multilayer polypropylene film of the present invention is a propylene homopolymer, or propylene and ethylene, 1-butene, 1- A copolymer mainly composed of propylene with an α-olefin such as hexene, 4-methyl / 1-pentene and 1-octene is modified by adding a polar group. Among them, those graft-modified with unsaturated carboxylic acid or derivatives thereof are preferable because they are excellent in the effect of improving the adhesion with the coating layer made of the polyurethane resin (D).
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。 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.
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。 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.
＜プロピレン重合体（Ｃ）＞
本発明の二軸延伸多層ポリプロピレンフィルムの裏面層を形成するプロピレン重合体（Ｃ）は、プロピレンの単独重合体、若しくはプロピレンと、他の少量、例えば、５モル％以下のα−オレフィン、例えば、エチレン、１−ブテン、１−ヘキセン、４−メチル・１−ペンテン、１−オクテン等とのランダム共重合体である。ランダム共重合体は、プロピレンと二種以上のα‐オレフィンからなる三元ランダム共重合体であってもよい。
<Propylene polymer (C)>
The propylene polymer (C) that forms the back layer of the biaxially oriented multilayer polypropylene film of the present invention is a propylene homopolymer or propylene and another small amount, for example, 5 mol% or less α-olefin, for example, Random copolymers with ethylene, 1-butene, 1-hexene, 4-methyl / 1-pentene, 1-octene and the like. The random copolymer may be a ternary random copolymer composed of propylene and two or more α-olefins.
本発明に係るプロピレン重合体（Ｃ）は、通常、ＭＦＲ（ＡＳＴＭ Ｄ１２３８ 荷重２１６０ｇ，温度２３０℃）が０．５ないし６０ｇ／１０分、好ましくは０．５ないし１０ｇ／１０分、より好ましくは１ないし５ｇ／１０分の範囲にある。 The propylene polymer (C) according to the present invention usually has an MFR (ASTM D1238 load 2160 g, temperature 230 ° C.) of 0.5 to 60 g / 10 minutes, preferably 0.5 to 10 g / 10 minutes, more preferably 1 Or in the range of 5 g / 10 min.
本発明に係るプロピレン重合体（Ｃ）として、プロピレン単独重合体とプロピレン・α‐オレフィンランダム共重合体との組成物を用いた場合は、接着性に優れる二軸延伸多層ポリプロピレンフィルムとなる。 When a composition of a propylene homopolymer and a propylene / α-olefin random copolymer is used as the propylene polymer (C) according to the present invention, a biaxially stretched multilayer polypropylene film having excellent adhesiveness is obtained.
本発明に係るプロピレン重合体（Ｃ）として、プロピレン・α‐オレフィンランダム共重合体を用いる場合は、プロピレン・α‐オレフィンランダム共重合体は、通常、融点が１００〜１５０℃、好ましくは１１０〜１４５℃の範囲にある。 When a propylene / α-olefin random copolymer is used as the propylene polymer (C) according to the present invention, the propylene / α-olefin random copolymer usually has a melting point of 100 to 150 ° C., preferably 110 to It is in the range of 145 ° C.
本発明に係るプロピレン重合体（Ｃ）として、プロピレン単独重合体とプロピレン・α−オレフィンランダム共重合体の組成物を用いる場合は、その量比は特に限定はされないが、通常、プロピレン単独重合体とプロピレン・α−オレフィンランダム共重合体の合計量１００質量％に対して、プロピレン単独重合体を４０〜９０質量％、好ましくは５０〜８０質量％含む。 When the composition of the propylene homopolymer and the propylene / α-olefin random copolymer is used as the propylene polymer (C) according to the present invention, the amount ratio is not particularly limited, but usually the propylene homopolymer. The propylene homopolymer is contained in an amount of 40 to 90% by mass, preferably 50 to 80% by mass, based on 100% by mass of the total amount of propylene / α-olefin random copolymer.
本発明に係るプロピレン重合体（Ｃ）には、上記プロピレン重合体組成物（Ａ）と同様に、必要に応じて、耐熱安定剤、耐候安定剤、紫外線吸収剤、滑剤、スリップ剤、核剤、ブロッキング防止剤、帯電防止剤、防曇剤、顔料、染料等の通常ポリオレフィンに用いる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おいてもよい。 In the propylene polymer (C) according to the present invention, a heat-resistant stabilizer, a weather-resistant stabilizer, an ultraviolet absorber, a lubricant, a slip agent, and a nucleating agent are added to the propylene polymer (C) as necessary. Various additives usually used for polyolefins such as an antiblocking agent, an antistatic agent, an antifogging agent, a pigment, and a dye may be added within a range that does not impair the object of the present invention.
＜ポリウレタン系樹脂（Ｄ）＞
本発明の二軸延伸多層ポリプロピレンフィルムの表面層に被覆されるポリウレタン系樹脂（Ｄ）は、一般にフィルムの接着剤として公知のポリウレタン系からなるドライラミネート、水性ドライラミネート、無溶剤ラミネート、電子線硬化型ラミネート接着剤として製造されているポリエステル系ポリウレタン、ポリエーテル系ポリウレタンあるいはポリウレタンポリ尿素樹脂等が挙げられる。かかるポリウレタン系樹脂は、水分散型または溶剤型のいずれでもよいが、ポリウレタン系樹脂被覆層の架橋度の調節が容易であり、また生産現場の作業環境の点から水分散型ポリウレタン系樹脂が好ましい。
<Polyurethane resin (D)>
The polyurethane resin (D) to be coated on the surface layer of the biaxially stretched multilayer polypropylene film of the present invention is generally a dry laminate, aqueous dry laminate, solventless laminate, electron beam curing made of polyurethane known as a film adhesive. Examples thereof include polyester-based polyurethane, polyether-based polyurethane, and polyurethane-polyurea resin that are manufactured as mold laminate adhesives. Such a polyurethane resin may be either water-dispersed or solvent-based, but it is easy to adjust the degree of crosslinking of the polyurethane-based resin coating layer, and water-dispersible polyurethane-based resins are preferable from the viewpoint of the working environment at the production site. .
本発明に係るポリウレタン系樹脂（Ｄ）は、好ましくはガラス転移温度（Ｔｇ）が３５℃以上、より好ましくは５０℃以上である。ポリウレタン系樹脂（Ｄ）として、Ｔｇが上記範囲のポリウレタン系樹脂を用いた場合は、耐ブロッキング性に優れる二軸延伸多層ポリプロピレンフィルムが得られるので好ましい。 The polyurethane resin (D) according to the present invention preferably has a glass transition temperature (Tg) of 35 ° C. or higher, more preferably 50 ° C. or higher. When a polyurethane resin having a Tg in the above range is used as the polyurethane resin (D), a biaxially stretched multilayer polypropylene film having excellent blocking resistance is obtained, which is preferable.
本発明に係るポリウレタン系樹脂（Ｄ）のＴｇは、種々公知の方法、例えば、ポリウレタン系樹脂（Ｄ）を構成するポリエーテルグリコール、あるいはポリエステルグリコール、あるいはイソシアネート化合物を種々選択することにより、得られ得る。 The Tg of the polyurethane resin (D) according to the present invention can be obtained by various known methods, for example, by selecting various polyether glycols, polyester glycols, or isocyanate compounds constituting the polyurethane resin (D). obtain.
また、かかるポリウレタン系樹脂（Ｄ）としては、種々市販のポリウレタン樹脂、例えば、三井化学株式会社から、水分散タイプのポリウレタン樹脂として、Ｔｇが異なる樹脂、具体的には、三井化学社製 商品名 タケラックＷＳ４０００（Ｔｇ＝１３６℃）、商品名 タケラックＷ６６０１（Ｔｇ＝１２４℃）、商品名 タケラックＷＳ５１００（Ｔｇ＝１２０℃）、商品名 タケラックＷ５０３０（Ｔｇ＝８０℃）および、商品名 タケラックＷＳ５０００（Ｔｇ＝６５℃）などを入手できる。 Moreover, as this polyurethane-type resin (D), various commercially available polyurethane resins, for example, Mitsui Chemical Co., Ltd., as a water dispersion type polyurethane resin, resin having different Tg, specifically, Mitsui Chemical Co., Ltd. Takelac WS4000 (Tg = 136 ° C.), trade name Takelac W6601 (Tg = 124 ° C.), trade name Takerak WS5100 (Tg = 120 ° C.), trade name Takerak W5030 (Tg = 80 ° C.) and trade name Takerak WS5000 (Tg = 65 ° C).
水分散型ポリウレタン系樹脂としては、ポリウレタン系樹脂の主鎖または側鎖にカルボン酸塩（−ＣＯＯＮａなど）、スルホン酸塩（−ＳＯ3Ｎａなど）等の親水基を導入した自己乳化型ポリウレタン系樹脂が好ましい。溶剤型の場合には、イソシアネート系樹脂を架橋剤に使用し、三次元構造を有したポリウレタンを形成するが、水分散型はリニアーなポリウレタンあるいはポリウレタンポリ尿素樹脂になっている場合が多いため、メラミン系樹脂、エポキシ系樹脂、イミン系樹脂等の架橋剤をポリウレタン系樹脂に対して３ないし１０質量％程度添加してもよいし、酸触媒を０．５ないし１質量％程度添加して硬化反応をより促進させることも出来る。かかる架橋剤は、易接着性皮膜の耐水性、耐溶剤性を向上させるだけでなく、接着性の向上にも寄与する。 Examples of water-dispersed polyurethane resins include self-emulsifying polyurethane resins in which hydrophilic groups such as carboxylates (such as —COONa) and sulfonates (such as —SO 3 Na) are introduced into the main chain or side chain of the polyurethane resin. Resins are preferred. In the case of the solvent type, an isocyanate resin is used as a crosslinking agent to form a polyurethane having a three-dimensional structure, but the water dispersion type is often a linear polyurethane or polyurethane polyurea resin, A crosslinking agent such as a melamine resin, an epoxy resin, or an imine resin may be added in an amount of about 3 to 10% by mass relative to the polyurethane resin, or an acid catalyst may be added in an amount of about 0.5 to 1% by mass to cure. The reaction can be further promoted. Such a crosslinking agent not only improves the water resistance and solvent resistance of the easy-adhesive film, but also contributes to an improvement in adhesion.
本発明に係るポリウレタン系樹脂（Ｄ）には、例えば、ブロッキングを防止するなどの目的で、必要に応じて、無機微粒子や有機微粒子等を添加してもよい。
＜二軸延伸多層ポリプロピレンフィルム＞
本発明の二軸延伸多層ポリプロピレンフィルムは、前記プロピレン重合体組成物（Ａ）から得られる二軸延伸フィルム基材層の片面に、前記変性プロピレン重合体（ｂ１）を含むプロピレン重合体（Ｂ）からなる表面層、及び他の片面に前記プロピレン重合体（Ｃ）からなる裏面層が積層されてなる。
For example, inorganic fine particles or organic fine particles may be added to the polyurethane-based resin (D) according to the present invention, for example, for the purpose of preventing blocking.
<Biaxially stretched multilayer polypropylene film>
The biaxially stretched multilayer polypropylene film of the present invention is a propylene polymer (B) containing the modified propylene polymer (b1) on one side of a biaxially stretched film substrate layer obtained from the propylene polymer composition (A). And a back layer made of the propylene polymer (C) is laminated on the other surface.
本発明の二軸延伸多層ポリプロピレンフィルムは、前記プロピレン重合体組成物（Ａ）から得られる二軸延伸フィルム基材層の片面に、前記変性プロピレン重合体（ｂ１）を含むプロピレン重合体（Ｂ）からなる表面層、当該表面層上に前記ポリウレタン系樹脂（Ｄ）からなる被覆層が積層され、他の片面に前記プロピレン重合体（Ｃ）からなる裏面層が積層されてなる。 The biaxially stretched multilayer polypropylene film of the present invention is a propylene polymer (B) containing the modified propylene polymer (b1) on one side of a biaxially stretched film substrate layer obtained from the propylene polymer composition (A). And a coating layer made of the polyurethane resin (D) is laminated on the surface layer, and a back layer made of the propylene polymer (C) is laminated on the other surface.
本発明の二軸延伸多層ポリプロピレンフィルムは、表面層の厚みが通常、０．５〜１０．０μｍ、好ましくは０．５〜５．０μｍ、二軸延伸フィルム基材層の厚みが通常、１９〜４９μｍ、好ましくは１９〜３９μｍ、裏面層の厚みが通常、０．５〜１０．０μｍ、好ましくは０．５〜５．０μｍの範囲にあり、二軸延伸多層ポリプロピレンフィルム全体の厚みが通常、１５〜５０μｍ、好ましくは１８〜４０μｍの範囲にある。 In the biaxially stretched multilayer polypropylene film of the present invention, the thickness of the surface layer is usually 0.5 to 10.0 μm, preferably 0.5 to 5.0 μm, and the thickness of the biaxially stretched film substrate layer is usually 19 to. 49 μm, preferably 19-39 μm, the thickness of the back layer is usually in the range of 0.5-10.0 μm, preferably 0.5-5.0 μm, and the total thickness of the biaxially oriented multilayer polypropylene film is usually 15 It is in the range of -50 μm, preferably 18-40 μm.
本発明の二軸延伸多層フィルムがポリウレタン系樹脂（Ｄ）からなる被覆層を有する場合は、被覆層の厚みが、通常、０．１〜１．０μｍ、好ましくは０．１〜０．５μｍの範囲にある。 When the biaxially stretched multilayer film of the present invention has a coating layer made of a polyurethane resin (D), the thickness of the coating layer is usually 0.1 to 1.0 μm, preferably 0.1 to 0.5 μm. Is in range.
本発明の二軸延伸多層ポリプロピレンフィルムとして、Ｔｇが３５℃以上のポリウレタン系樹脂からなる被覆層を有する場合は、プロピレン重合体（Ｂ）からなる表面層には、ブロッキング防止剤を添加する必要はなく、添加した場合でも、０．０１質量％未満を好ましく選択できる。ポリウレタン系樹脂のＴｇとしては５０℃以上がさらに好ましく、１００℃以上がより好ましい。Ｔｇが高いポリウレタン系樹脂を用いるほど得られる二軸延伸多層ポリプロピレンフィルムの耐ブロッキング性が向上し、かつ酸素透過度が小さくなるからである。 When the biaxially oriented multilayer polypropylene film of the present invention has a coating layer made of a polyurethane resin having a Tg of 35 ° C. or higher, it is necessary to add an antiblocking agent to the surface layer made of the propylene polymer (B). Even when added, less than 0.01% by mass can be preferably selected. The Tg of the polyurethane resin is more preferably 50 ° C. or higher, and more preferably 100 ° C. or higher. This is because the blocking resistance of the biaxially stretched multilayer polypropylene film obtained as the polyurethane-based resin having a higher Tg is improved, and the oxygen permeability is reduced.
本発明の二軸延伸多層ポリプロピレンフィルムは、通常、密度が０．５〜０．９ｇ／ｃｍ3、好ましくは０．５２〜０．７９ｇ／ｃｍ3、ヘイズ（曇価）が、通常、８５％以上、好ましくは８９％以上、全光線透過率が通常、３０％以下、好ましくは２５％以下、表面層の表面光沢度が通常、５０％以上、好ましくは６０％以上、裏面層の表面光沢度が通常、４０％以上、好ましくは４５％以上、表面層の表面粗度が通常、０．０５〜０．２０μｍ、好ましくは０．０７〜０．１９μｍ、裏面層の表面粗度が通常、０．０５〜０．２０μｍ、好ましくは０．０７〜０．１９μｍ、白色度（Ｌ＊値）が通常、８５以上、好ましくは８９以上の範囲にある。 The biaxially oriented multilayer polypropylene film of the present invention usually has a density of 0.5 to 0.9 g / cm 3 , preferably 0.52 to 0.79 g / cm 3 and a haze (cloudiness) of usually 85%. Above, preferably 89% or more, total light transmittance is usually 30% or less, preferably 25% or less, surface gloss of surface layer is usually 50% or more, preferably 60% or more, surface gloss of back layer Is usually 40% or more, preferably 45% or more, the surface roughness of the surface layer is usually 0.05 to 0.20 μm, preferably 0.07 to 0.19 μm, and the surface roughness of the back layer is usually 0. 0.05 to 0.20 μm, preferably 0.07 to 0.19 μm, and the whiteness (L * value) is usually 85 or more, preferably 89 or more.
本発明の二軸延伸多層ポリプロピレンフィルムは、プロピレン重合体組成物（Ａ）から得られる二軸延伸フィルムからなる基材層は、通常、空隙率が５％以上である。
本発明の二軸延伸多層ポリプロピレンフィルムは、水蒸気透過度が通常、３．０〜１５．０ｇ／ｍ2／ｄａｙ、好ましくは４．０〜１３．０ｇ／ｍ2／ｄａｙ、酸素透過度が通常、５０〜１０００ｃｃ／ｍ2／ｄａｙ、好ましくは７０〜８００ｃｃ／ｍ2／ｄａｙの範囲にある。
In the biaxially stretched multilayer polypropylene film of the present invention, the base material layer made of the biaxially stretched film obtained from the propylene polymer composition (A) usually has a porosity of 5% or more.
The biaxially stretched multilayer polypropylene film of the present invention has a water vapor transmission rate of usually 3.0 to 15.0 g / m 2 / day, preferably 4.0 to 13.0 g / m 2 / day, and has a normal oxygen transmission rate. 50 to 1000 cc / m 2 / day, preferably 70 to 800 cc / m 2 / day.
本発明の二軸延伸多層ポリプロピレンフィルムは、必要に応じて片面あるいは両面をコロナ処理、火炎処理等の表面処理をしてもよい。また、用途により、ヒートシール性を付与するために高圧法低密度ポリエチレン、線状低密度ポリエチレン、結晶性あるいは低結晶性のエチレンと炭素数３ないし１０のα−オレフィンとのランダム共重合体あるいはプロピレンとエチレン若しくは炭素数４以上のα−オレフィンとのランダム共重合体、ポリブテン、エチレン・酢酸ビニル共重合体等の低融点のポリマーを単独あるいはそれらの組成物からなるフィルムを裏面層に積層してもよい。 The biaxially stretched multilayer polypropylene film of the present invention may be subjected to surface treatment such as corona treatment or flame treatment on one or both sides as necessary. Depending on the application, in order to impart heat sealability, a high pressure process low density polyethylene, linear low density polyethylene, a random copolymer of crystalline or low crystalline ethylene and an α-olefin having 3 to 10 carbon atoms, or Laminate a low-melting point polymer such as a random copolymer of propylene and ethylene or an α-olefin having 4 or more carbon atoms, polybutene, ethylene / vinyl acetate copolymer, or a film made of these compositions on the back layer. May be.
＜二軸延伸多層ポリプロピレンフィルムの製造方法＞
本発明の二軸延伸多層ポリプロピレンフィルムは、種々公知の方法、例えば、二軸延伸フィルム基材層となる前記プロピレン重合体組成物（Ａ）、表面層となる前記変性プロピレン重合体（ｂ１）を含むプロピレン重合体（Ｂ）及び裏面層となる前記プロピレン重合体（Ｃ）とを共押出し成形して得た多層シートを、公知の同時二軸延伸法あるいは逐次二軸延伸法等の二軸延伸フィルム製造方法により得られる。二軸延伸の条件は、公知の二軸延伸ポリプロピレンの製造条件、例えば、逐次二軸延伸法では、縦延伸温度１００℃〜１４５℃、延伸倍率を４〜７倍の範囲、横延伸温度を１５０〜１９０℃、延伸倍率を８〜１１倍の範囲にすればよい。
<Method for producing biaxially stretched multilayer polypropylene film>
The biaxially stretched multilayer polypropylene film of the present invention is obtained by various known methods, for example, the propylene polymer composition (A) serving as a biaxially stretched film substrate layer and the modified propylene polymer (b1) serving as a surface layer. A multilayer sheet obtained by coextrusion molding of the propylene polymer (B) containing and the propylene polymer (C) to be the back layer is subjected to biaxial stretching such as a known simultaneous biaxial stretching method or sequential biaxial stretching method. It is obtained by a film manufacturing method. The biaxial stretching conditions are known biaxially oriented polypropylene production conditions, for example, in the sequential biaxial stretching method, the longitudinal stretching temperature is 100 ° C. to 145 ° C., the stretching ratio is in the range of 4 to 7 times, and the transverse stretching temperature is 150. What is necessary is just to make -190 degreeC and a draw ratio into the range of 8-11 times.
表面層にポリウレタン系樹脂（Ｄ）からなる被覆層を積層する場合は、前記変性プロピレン重合体（ｂ１）を含むプロピレン重合体（Ｂ）からなる表面層上に、例えば、前記ポリウレタン樹脂（Ｄ）の水溶液あるいは分散液を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コーター、アークグラビアコーター、グラビアリバース及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及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のそれ自体公知の塗工機を用いて、ポリウレタン系樹脂（Ｄ）の水溶液中に含まれる組成物の量で０．１ないし２０ｇ／ｍ2、好ましくは０．１ないし１．５ｇ／ｍ2となるように塗布した後、５０ないし１４０℃の温度で３秒以上乾燥することにより得られる。 When a coating layer made of a polyurethane resin (D) is laminated on the surface layer, for example, the polyurethane resin (D) is formed on the surface layer made of the propylene polymer (B) containing the modified propylene polymer (b1). Air knife coater, direct gravure coater, gravure offset coater, arc gravure coater, gravure reverse and jet nozzle type gravure coater, top feed reverse coater, bottom feed reverse coater and nozzle feed reverse coater etc. The amount of the composition contained in the aqueous solution of the polyurethane resin (D) using various coating machines known per se, such as a roll coater, 5-roll coater, lip coater, bar coater, bar reverse coater, die coater. so .1 to 20 g / m 2, preferably after application so that 1.5 g / m 2 to 0.1, and drying at least 3 seconds at a temperature of 50 to 140 ° C..
表面層にポリウレタン系樹脂（Ｄ）からなる被覆層を積層する方法としては、上記記載の方法で多層の二軸延伸フィルムを延伸した後、引続き、上記方法で表面層にポリウレタン系樹脂（Ｄ）を被覆する方法（インラインコート法）、あるいは、一旦、上記記載の方法で多層の二軸延伸フィルムを製造した後、別途、上記方法で表面層にポリウレタン系樹脂（Ｄ）を被覆する方法（オフラインコート法）など、種々公知の製造方法を採り得る。 As a method of laminating a coating layer made of a polyurethane resin (D) on the surface layer, a multilayer biaxially stretched film is stretched by the method described above, and then the polyurethane resin (D) is applied to the surface layer by the above method. A method of coating a polyurethane resin (D) on the surface layer by the above method after manufacturing a multi-layer biaxially stretched film by the above-described method (offline) Various known production methods such as a coating method can be employed.
また、表面層にポリウレタン系樹脂（Ｄ）からなる被覆層を積層する前に、ポリウレタン系樹脂（Ｄ）との接着性を改良するために、種々公知の方法、例えば、コロナ処理、火炎処理、あるいは、芳香族エステル系、有機チタネート系、あるいはポリエチレンイミン系などをアンカー層としてコート（プライマー処理）しておいてもよい。 In addition, before laminating a coating layer made of polyurethane resin (D) on the surface layer, various known methods such as corona treatment, flame treatment, Or you may coat (primer process) an aromatic ester type | system | group, an organic titanate type | system | group, or a polyethyleneimine type | system | group as an anchor layer.
次に実施例を挙げて本発明を更に具体的に説明するが、本発明はその要旨を越えない限りこれらの実施例に制約されるものではない。
実施例及び比較例における物性値等は、以下の評価方法により求めた。
EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples unless it exceeds the gist.
The physical property values and the like in Examples and Comparative Examples were obtained by the following evaluation methods.
（１）空隙率（％）
二軸延伸多層ポリプロピレンフィルムの空隙率は、以下の計算式から算出した。
各層の密度＝積層した各層のｍ2当たり重量／積層した各層の厚み
空隙率＝（１−各層の密度／空隙を形成しない二軸延伸多層ポリプロピレンフィルムの密度）×１００
（２）密度（ｇ／ｃｍ3）
二軸延伸多層ポリプロピレンフィルムの厚みおよび１ｍ２あたりのフィルム重量を測定することにより算出した。
(1) Porosity (%)
The porosity of the biaxially stretched multilayer polypropylene film was calculated from the following formula.
Density of each layer = weight per m 2 of each laminated layer / thickness of each laminated layer Porosity = (1−density of each layer / density of biaxially stretched multilayer polypropylene film not forming voids) × 100
(2) Density (g / cm 3 )
The thickness was calculated by measuring the thickness of the biaxially stretched multilayer polypropylene film and the film weight per 1 m 2.
（３）Ｈａｚｅ（曇価）（％）
二軸延伸多層ポリプロピレンフィルムのＨａｚｅは、ＨａｚｅＭｅｔｅｒ（日本電色工業社製ＶＧＳ−１Ｄ−３００Ａ）を使用して、フィルム１枚のＨａｚｅをＪＩＳ Ｋ ７１０５の試験を行うことにより測定した。
(3) Haze (cloudiness value) (%)
The haze of the biaxially stretched multilayer polypropylene film was measured by carrying out a JIS K 7105 test for one film using a HazeMeter (Nippon Denshoku Industries Co., Ltd. VGS-1D-300A).
（４）全光線透過率（％）
二軸延伸多層ポリプロピレンフィルムの全光線透過率は、ＨａｚｅＭｅｔｅｒ（日本電色工業社製ＶＧＳ−１Ｄ−３００Ａ）を使用して、フィルム１枚の全光線透過率をＪＩＳ Ｋ ７１０５の試験を行うことにより測定した。
(4) Total light transmittance (%)
The total light transmittance of the biaxially stretched multilayer polypropylene film is obtained by conducting a JIS K 7105 test on the total light transmittance of one film using HazeMeter (VGS-1D-300A manufactured by Nippon Denshoku Industries Co., Ltd.). It was measured.
（５）表面光沢度（％／６０°）
（表面層及び裏面層）
二軸延伸多層ポリプロピレンフィルムの表面光沢度を、ＨａｚｅＭｅｔｅｒ（日本電色工業社製ＶＧＳ−１Ｄ−３００Ａ）を使用して、入射角６０度でＪＩＳ Ｋ ７１０５の試験を行うことにより測定した。
(5) Surface glossiness (% / 60 °)
(Surface layer and back layer)
The surface glossiness of the biaxially stretched multilayer polypropylene film was measured by performing a JIS K 7105 test at an incident angle of 60 degrees using HazeMeter (Nippon Denshoku Industries Co., Ltd. VGS-1D-300A).
（６）表面粗度（μｍ）
三次元表面粗さ測定器（小坂研究所製ＳＥ−３０ＫＳ）および解析装置（小坂研究所製ＴＤＡ−２１）を使用して三次元中心面平均粗さＳＲａを測定した。
(6) Surface roughness (μm)
Three-dimensional center surface average roughness SRa was measured using a three-dimensional surface roughness measuring instrument (SE-30KS manufactured by Kosaka Laboratory) and an analyzer (TDA-21 manufactured by Kosaka Laboratory).
（７）熱収縮率（％）
二軸延伸多層プリプロピレンフィルムの熱収縮率は、ＭＤ方向に１００ｍｍ×ＴＤ方向に１００ｍｍの正方形に切り出したサンプル片を、１２０度のオーブンに３０分静置し、オーブンから取り出した後、室温にてサンプル片のＭＤ方向およびＴＤ方向の寸法を測定した。測定した値を使用し、以下の計算式から熱収縮率を算出した。
熱収縮値＝（オーブンに静置する前のサンプル片の寸法−オーブンに静置後、室温で測定したサンプル片の寸法）／オーブンに静置する前のサンプル片の寸法×１００
(7) Thermal shrinkage (%)
The heat shrinkage rate of the biaxially stretched multi-layer propylene film was determined by placing a sample piece cut into a 100 mm square in the MD direction and a 100 mm square in the TD direction in a 120 degree oven for 30 minutes, taking it out of the oven, and The dimensions of the sample pieces in the MD direction and the TD direction were measured. Using the measured values, the heat shrinkage rate was calculated from the following formula.
Heat shrinkage value = (size of sample piece before standing in oven−size of sample piece measured at room temperature after standing in oven) / size of sample piece before standing in oven × 100
（８）白色度
白紙上に二軸延伸多層ポリプロピレンフィルム１０枚を重ね合わせ、ＳｐｅｃｔｒｏＥｙｅ（Ｇｒｅｔａｇ Ｍａｃｂｅｔｈ社製）を使用してＬ＊値を測定した。
(8) Whiteness Ten biaxially stretched multilayer polypropylene films were superposed on white paper, and L * values were measured using SpectroEye (manufactured by Gretag Macbeth).
（９）水蒸気透過度〔ｇ／（ｍ2・ｄａｙ）〕
二軸延伸多層プリプロピレンフィルムを折り返し、２方をヒートシールして袋状にした後、内容物として塩化カルシウムを入れ、もう一方をヒートシールにより、表面積が０．０１ｍ２になるように袋を作成し、これを４０℃、９０％Ｒ．Ｈ．の条件で７２時間放置し、その重量差で水蒸気透過度を測定した。
(9) Water vapor permeability [g / (m 2 · day)]
Fold the biaxially stretched multilayer polypropylene film, heat seal the two sides into a bag shape, add calcium chloride as the contents, and heat seal the other to create a bag with a surface area of 0.01 m2. This was treated at 40 ° C. and 90% R.D. H. The sample was allowed to stand for 72 hours under the above conditions, and the water vapor permeability was measured based on the weight difference.
（１０）酸素透過度（ｃｃ／（ｍ2・ｄａｙ））
二軸延伸多層ポリプロピレンフィルムを、モコン社製ＯＸ−ＴＲＡＮ２／２１ ＭＬを用いて、ＪＩＳ Ｋ ７１２６（等圧法）に準じ、温度２０℃、湿度９０％Ｒ．Ｈ．の条件に３時間調整した後に酸素透過度を測定した。
(10) Oxygen permeability (cc / (m 2 · day))
A biaxially stretched multilayer polypropylene film was tempered at 20 ° C. and 90% humidity according to JIS K 7126 (isobaric method) using OX-TRAN2 / 21 ML manufactured by Mocon. H. After adjusting to these conditions for 3 hours, the oxygen permeability was measured.
実施例および比較例で用いたプロピレン重合体などを以下に示す。
（１）プロピレン重合体（ａ１）、（Ｂ）および（Ｃ）
（１−１）プロピレン単独重合体（ＰＰ−１）：融点＝１６０℃、ＭＦＲ＝３．０ｇ／１０分。
（１−２）プロピレン・エチレンランダム共重合体（ＰＰ−２）：融点＝１４２℃、ＭＦＲ＝７．０ｇ／１０分。
The propylene polymers used in Examples and Comparative Examples are shown below.
(1) Propylene polymer (a1), (B) and (C)
(1-1) Propylene homopolymer (PP-1): Melting point = 160 ° C., MFR = 3.0 g / 10 min.
(1-2) Propylene / ethylene random copolymer (PP-2): melting point = 142 ° C., MFR = 7.0 g / 10 min.
（２）変性プロピレン重合体（ｂ１）
（２−１）無水マレイン酸グラフト変性プロピレン単独重合体（ＰＰ−３）
三井化学（株） 商品名 アドマー 融点＝１６０℃、ＭＦＲ＝３．０ｇ／１０分。
(2) Modified propylene polymer (b1)
(2-1) Maleic anhydride graft-modified propylene homopolymer (PP-3)
Mitsui Chemicals, Inc. Trade name Admer Melting point = 160 ° C., MFR = 3.0 g / 10 min.
（３）ポリウレタン系樹脂（Ｄ）
（３−１）三井化学（株）製 商品名 タケラックＷ６６０１（Ｔｇ＝１２４℃）
（４）炭酸カルシウム
平均粒子径：１．２μｍ、最大粒子径：５．０μｍ、９０％累積頻度粒径が２．５μｍ、水分量４００ｐｐｍ以下（カールフィッシャー法、２００℃で測定）のステアリン酸でコーティングされた炭酸カルシウム粉末。
(3) Polyurethane resin (D)
(3-1) Trade name Takerak W6601 (Tg = 124 ° C.) manufactured by Mitsui Chemicals, Inc.
(4) Calcium carbonate Stearic acid having an average particle size of 1.2 μm, a maximum particle size of 5.0 μm, a 90% cumulative frequency particle size of 2.5 μm, and a water content of 400 ppm or less (measured at Karl Fischer method at 200 ° C.) Coated calcium carbonate powder.
（５）酸化チタン
平均粒子径：０．２μｍ、水分量４００ｐｐｍ以下（カールフィッシャー法、２００℃で測定）のアルミナ処理されたルチル型酸化チタン粉末。
(5) Titanium oxide An alumina-treated rutile type titanium oxide powder having an average particle size of 0.2 μm and a water content of 400 ppm or less (Karl Fischer method, measured at 200 ° C.).
〔実施例１〕
＜基材層：プロピレン重合体組成物層＞
前記ＰＰ−１、ＰＰ−１に予め炭酸カルシウムを混練した組成物およびＰＰ−１に予め酸化チタンを混練した組成物を用意し、当該成分をドライブレンドして、ＰＰ−１を９２．８質量％、炭酸カルシウムを６．０質量％、および酸化チタンを１．２質量％含む基材層用プロピレン重合体組成物を用意した。
[Example 1]
<Base material layer: Propylene polymer composition layer>
A composition in which calcium carbonate was previously kneaded with PP-1 and PP-1 and a composition in which titanium oxide was kneaded in advance with PP-1 were prepared, and the components were dry-blended to obtain 92.8 masses of PP-1. %, A propylene polymer composition for a base material layer containing 6.0% by mass of calcium carbonate and 1.2% by mass of titanium oxide was prepared.
＜表面層：プロピレン系重合体層＞
前記ＰＰ−２およびＰＰ−３をドライブレンドして、ＰＰ−２を３０質量％、およびＰＰ−３を７０質量％含む表面層用プロピレン系重合体組成物を用意した。
<Surface layer: Propylene polymer layer>
The PP-2 and PP-3 were dry blended to prepare a propylene polymer composition for a surface layer containing 30% by mass of PP-2 and 70% by mass of PP-3.
＜裏面層：プロピレン系重合体層＞
前記ＰＰ−１およびＰＰ−２をドライブレンドして、ＰＰ−１を７０質量％、ＰＰ−２を３０質量％含む裏面層用プロピレン系重合体組成物を用意した。
<Back layer: Propylene polymer layer>
The PP-1 and PP-2 were dry blended to prepare a propylene polymer composition for the back layer containing 70% by mass of PP-1 and 30% by mass of PP-2.
＜二軸延伸多層ポリプロピレンフィルムの製造＞
前記表面層用プロピレン系重合体組成物、基材層用プロピレン重合体組成物及び裏面層用プロピレン系重合体組成物を押出量比（表面層／基材層／裏面層：１／５８．４／１）になるよう各々スクリュー押出機を用いて溶融押出し、マルチマニホールドタイプＴ−ダイから押出後、冷却ロール上にて急冷し厚さ約１．５ｍｍの多層シートを得た。このシートを１１０℃で加熱しフィルムの流れ方向（縦方向）に５倍延伸した。この５倍延伸したシートを１６０℃で加熱し流れ方向に対して直交する方向（横方向）に１０倍延伸して、基層の厚さ：３６．２μｍ、表面層の厚さ：０．５μｍ、裏面層の厚さ：０．５μｍ（合計フィルム厚さ：３７．２μｍ）の二軸延伸ポリプロピレン多層フィルムを得た。二軸延伸ポリプロピレン多層フィルムの表面層には、以下の方法で被覆層を設け、裏面層には、コロナ処理を施した。かかる二軸延伸多層ポリプロピレンフィルムの物性等を前記記載の方法で測定した。評価結果を表１に示す。
<Manufacture of biaxially oriented multilayer polypropylene film>
Extrusion ratio (surface layer / base material layer / back surface layer: 1 / 58.4) of the propylene polymer composition for surface layer, the propylene polymer composition for base material layer, and the propylene polymer composition for back surface layer. 1) Each was melt extruded using a screw extruder, extruded from a multi-manifold type T-die, and then rapidly cooled on a cooling roll to obtain a multilayer sheet having a thickness of about 1.5 mm. This sheet was heated at 110 ° C. and stretched 5 times in the film flow direction (longitudinal direction). The sheet stretched 5 times was heated at 160 ° C. and stretched 10 times in the direction perpendicular to the flow direction (lateral direction). The thickness of the base layer: 36.2 μm, the thickness of the surface layer: 0.5 μm, A biaxially oriented polypropylene multilayer film having a thickness of the back layer: 0.5 μm (total film thickness: 37.2 μm) was obtained. The surface layer of the biaxially oriented polypropylene multilayer film was provided with a coating layer by the following method, and the back layer was subjected to corona treatment. The physical properties of the biaxially stretched multilayer polypropylene film were measured by the method described above. The evaluation results are shown in Table 1.
＜被覆層：ポリウレタン系樹脂層＞
６．３％ポリウレタン溶液を用意し、グラビアロール式コーターにて固形分が０．１ｇ／ｍ２になるように表面層に塗布し、熱風乾燥器を使用し乾燥した。
<Coating layer: polyurethane resin layer>
A 6.3% polyurethane solution was prepared, applied to the surface layer with a gravure roll coater so that the solid content was 0.1 g / m 2, and dried using a hot air dryer.
〔実施例２〕
＜基材層：プロピレン重合体組成物層＞
前記ＰＰ−１、ＰＰ−２、ＰＰ−１に予め炭酸カルシウムを混練した組成物、およびＰＰ−１に予め酸化チタンを混練した組成物を用意し、当該成分をドライブンレドして、ＰＰ−１を６４．４質量％、ＰＰ−２を２１．５質量％、炭酸カルシウムを１３．１質量％、酸化チタンを１．０質量％含むプロピレン重合体組成物を用意した。
[Example 2]
<Base material layer: Propylene polymer composition layer>
A composition in which calcium carbonate is previously kneaded with PP-1, PP-2, PP-1 and a composition in which titanium oxide is kneaded in advance with PP-1 are prepared. A propylene polymer composition comprising 14.4% by mass, 21.5% by mass of PP-2, 13.1% by mass of calcium carbonate, and 1.0% by mass of titanium oxide was prepared.
＜表面層：プロピレン系重合体層＞
前記ＰＰ−２およびＰＰ−３をドライブレンドして、ＰＰ−２を５０質量％、およびＰＰ−３を５０質量％含む表面層用プロピレン系重合体組成物を用意した。
<Surface layer: Propylene polymer layer>
The PP-2 and PP-3 were dry blended to prepare a propylene polymer composition for a surface layer containing 50% by mass of PP-2 and 50% by mass of PP-3.
＜裏面層：プロピレン系重合体層＞
前記ＰＰ−１およびＰＰ−２をドライブレンドして、前記ＰＰ−１を３０質量％、ＰＰ−２を７０質量％含む裏面層用プロピレン系重合体組成物を用意した。
<Back layer: Propylene polymer layer>
The PP-1 and PP-2 were dry blended to prepare a propylene-based polymer composition for back layer containing 30% by mass of PP-1 and 70% by mass of PP-2.
＜二軸延伸多層ポリプロピレンフィルムの製造＞
前記表面層用プロピレン系重合体組成物、基材層用プロピレン重合体組成物及び裏面層用プロピレン系重合体組成物を押出量比（表面層／基材層／裏面層：１．６／５０．３／１）になるよう各々スクリュー押出機を用いて溶融押出し、マルチマニホールドタイプＴ−ダイから押出後、冷却ロール上にて急冷し厚さ約１．５ｍｍの多層シートを得た。このシートを１１０℃で加熱しフィルムの流れ方向（縦方向）に５倍延伸した。この５倍延伸したシートを１６０℃で加熱し流れ方向に対して直交する方向（横方向）に１０倍延伸して、基層の厚さ：３４．２μｍ、表面層の厚さ：０．８μｍ、裏面層の厚さ：０．５μｍ（合計フィルム厚さ：３５．５μｍ）の二軸延伸ポリプロピレン多層フィルムを得た。二軸延伸ポリプロピレン多層フィルムの表面層には、以下の方法で被覆層を設け、裏面層には、コロナ処理を施した。かかる二軸延伸多層ポリプロピレンフィルムの物性等を前記記載の方法で測定した。評価結果を表１に示す。
<Manufacture of biaxially oriented multilayer polypropylene film>
The extrusion ratio of the propylene polymer composition for the surface layer, the propylene polymer composition for the substrate layer and the propylene polymer composition for the back surface layer (surface layer / base material layer / back surface layer: 1.6 / 50) .3 / 1) were each melt extruded using a screw extruder, extruded from a multi-manifold type T-die, and then rapidly cooled on a cooling roll to obtain a multilayer sheet having a thickness of about 1.5 mm. This sheet was heated at 110 ° C. and stretched 5 times in the film flow direction (longitudinal direction). The sheet stretched 5 times was heated at 160 ° C. and stretched 10 times in the direction perpendicular to the flow direction (transverse direction), the thickness of the base layer: 34.2 μm, the thickness of the surface layer: 0.8 μm, A biaxially oriented polypropylene multilayer film having a thickness of the back layer: 0.5 μm (total film thickness: 35.5 μm) was obtained. The surface layer of the biaxially oriented polypropylene multilayer film was provided with a coating layer by the following method, and the back layer was subjected to corona treatment. The physical properties of the biaxially stretched multilayer polypropylene film were measured by the method described above. The evaluation results are shown in Table 1.
＜被覆層：ポリウレタン系樹脂層＞
６．３％ポリウレタン溶液を用意し、グラビアロール式コーターにて固形分が０．１ｇ／ｍ２になるように表面層に塗布し、熱風乾燥器を使用し乾燥した。
<Coating layer: polyurethane resin layer>
A 6.3% polyurethane solution was prepared, applied to the surface layer with a gravure roll coater so that the solid content was 0.1 g / m 2, and dried using a hot air dryer.
〔実施例３〕
＜基材層：プロピレン重合体組成物層＞
前記ＰＰ−１、ＰＰ−２、ＰＰ−１に予め炭酸カルシウムを混練した組成物およびＰＰ−１に予め酸化チタンを混練した組成物を用意し、当該成分をドライブレンドして、ＰＰ−１を６４．２質量％、ＰＰ−２を２１．４質量％、炭酸カルシウムを１２．１質量％、および酸化チタンを２．２質量％含むプロピレン重合体組成物を用意した。
Example 3
<Base material layer: Propylene polymer composition layer>
A composition in which calcium carbonate is previously kneaded with PP-1, PP-2, PP-1 and a composition in which titanium oxide is kneaded in advance with PP-1 are prepared. A propylene polymer composition containing 64.2% by mass, 21.4% by mass of PP-2, 12.1% by mass of calcium carbonate, and 2.2% by mass of titanium oxide was prepared.
＜表面層：プロピレン系重合体層＞
前記ＰＰ−２およびＰＰ−３をドライブレンドして、ＰＰ−２を５０質量％、およびＰＰ−３を５０質量％含む表面層用プロピレン系重合体組成物を用意した。
<Surface layer: Propylene polymer layer>
The PP-2 and PP-3 were dry blended to prepare a propylene polymer composition for a surface layer containing 50% by mass of PP-2 and 50% by mass of PP-3.
＜裏面層：プロピレン系重合体層＞
前記ＰＰ−１およびＰＰ−２をドライブレンドして、ＰＰ−１を３０質量％、ＰＰ−２を７０質量％含む裏面層用プロピレン系重合体組成物を用意した。
<Back layer: Propylene polymer layer>
The PP-1 and PP-2 were dry blended to prepare a propylene-based polymer composition for back layer containing 30% by mass of PP-1 and 70% by mass of PP-2.
＜二軸延伸多層ポリプロピレンフィルムの製造＞
前記表面層用プロピレン系重合体組成物、基材層用プロピレン重合体組成物及び裏面層用プロピレン系重合体組成物を押出量比（表面層／基材層／裏面層：９．１／２２．３／１）になるよう各々スクリュー押出機を用いて溶融押出し、マルチマニホールドタイプＴ−ダイから押出後、冷却ロール上にて急冷し厚さ約１．０ｍｍの多層シートを得た。このシートを１１０℃で加熱しフィルムの流れ方向（縦方向）に５倍延伸した。この５倍延伸したシートを１６０℃で加熱し流れ方向に対して直交する方向（横方向）に１０倍延伸して、基層の厚さ：１８．３μｍ、表面層の厚さ：４．３μｍ、裏面層の厚さ：０．５μｍ（合計フィルム厚さ：２３．１μｍ）の二軸延伸ポリプロピレン多層フィルムを得た。二軸延伸ポリプロピレン多層フィルムの表面層には、以下の方法で被覆層を設け、裏面層には、コロナ処理を施した。かかる二軸延伸多層ポリプロピレンフィルムの物性等を前記記載の方法で測定した。評価結果を表１に示す。
<Manufacture of biaxially oriented multilayer polypropylene film>
The extrusion ratio of the propylene polymer composition for the surface layer, the propylene polymer composition for the substrate layer, and the propylene polymer composition for the back layer (surface layer / substrate layer / back layer: 9.1 / 22) .3 / 1) were each melt extruded using a screw extruder, extruded from a multi-manifold type T-die, and then rapidly cooled on a cooling roll to obtain a multilayer sheet having a thickness of about 1.0 mm. This sheet was heated at 110 ° C. and stretched 5 times in the film flow direction (longitudinal direction). The sheet stretched 5 times was heated at 160 ° C. and stretched 10 times in the direction perpendicular to the flow direction (lateral direction). The thickness of the base layer: 18.3 μm, the thickness of the surface layer: 4.3 μm, A biaxially oriented polypropylene multilayer film having a thickness of the back surface layer of 0.5 μm (total film thickness: 23.1 μm) was obtained. The surface layer of the biaxially oriented polypropylene multilayer film was provided with a coating layer by the following method, and the back layer was subjected to corona treatment. The physical properties of the biaxially stretched multilayer polypropylene film were measured by the method described above. The evaluation results are shown in Table 1.
＜被覆層：ポリウレタン系樹脂層＞
６．３％ポリウレタン溶液を用意し、グラビアロール式コーターにて固形分が０．１ｇ／ｍ2になるように表面層に塗布し、熱風乾燥器を使用し乾燥した。
<Coating layer: polyurethane resin layer>
A 6.3% polyurethane solution was prepared, applied to the surface layer with a gravure roll coater so that the solid content was 0.1 g / m 2 , and dried using a hot air dryer.
〔比較例１〕
＜基材層：プロピレン重合体組成物層＞
前記ＰＰ−１、ＰＰ−１に予め炭酸カルシウムを混練した組成物およびＰＰ−１に予め酸化チタンを混練した組成物を用意し、当該成分をドライブレンドして、ＰＰ−１を９２．８質量％、炭酸カルシウムを６．０質量％、および酸化チタンを１．２質量％含む基材層用プロピレン重合体組成物を用意した。
[Comparative Example 1]
<Base material layer: Propylene polymer composition layer>
A composition in which calcium carbonate was previously kneaded with PP-1 and PP-1 and a composition in which titanium oxide was kneaded in advance with PP-1 were prepared, and the components were dry-blended to obtain 92.8 masses of PP-1. %, A propylene polymer composition for a base material layer containing 6.0% by mass of calcium carbonate and 1.2% by mass of titanium oxide was prepared.
＜表面層：プロピレン系重合体層＞
前記ＰＰ−２およびＰＰ−３をドライブレンドして、ＰＰ−２を３０質量％、およびＰＰ−３を７０質量％含む表面層用プロピレン系重合体組成物を用意した。
<Surface layer: Propylene polymer layer>
The PP-2 and PP-3 were dry blended to prepare a propylene polymer composition for a surface layer containing 30% by mass of PP-2 and 70% by mass of PP-3.
＜裏面層：プロピレン系重合体層＞
前記ＰＰ−１およびＰＰ−２をドライブレンドして、前記ＰＰ−１を７０質量％、およびＰＰ−２を３０質量％含む裏面層用プロピレン系重合体組成物を用意した。
<Back layer: Propylene polymer layer>
The PP-1 and PP-2 were dry blended to prepare a propylene-based polymer composition for the back layer containing 70% by mass of PP-1 and 30% by mass of PP-2.
＜二軸延伸多層ポリプロピレンフィルムの製造＞
前記表面層用プロピレン系重合体組成物、基材層用プロピレン重合体組成物及び裏面層用プロピレン系重合体組成物を押出量比（表面層／基材層／裏面層：１／５７．０／１）になるよう各々スクリュー押出機を用いて溶融押出し、マルチマニホールドタイプＴ−ダイから押出後、冷却ロール上にて急冷し厚さ約１．５ｍｍの多層シートを得た。このシートを１１０℃で加熱しフィルムの流れ方向（縦方向）に５倍延伸した。この５倍延伸したシートを１６０℃で加熱し流れ方向に対して直交する方向（横方向）に１０倍延伸して、基層の厚さ：３８．５μｍ、表面層の厚さ：０．５μｍ、裏面層の厚さ：０．５μｍ（合計フィルム厚さ：３７．２μｍ）の二軸延伸ポリプロピレン多層フィルムを得た。二軸延伸ポリプロピレン多層フィルムの表面層、裏面層には、コロナ処理を施した。かかる二軸延伸多層ポリプロピレンフィルムの物性等を前記記載の方法で測定した。評価結果を表１に示す。
<Manufacture of biaxially oriented multilayer polypropylene film>
The extrusion ratio of the propylene polymer composition for the surface layer, the propylene polymer composition for the substrate layer and the propylene polymer composition for the back surface layer (surface layer / base material layer / back surface layer: 1 / 57.0) 1) Each was melt extruded using a screw extruder, extruded from a multi-manifold type T-die, and then rapidly cooled on a cooling roll to obtain a multilayer sheet having a thickness of about 1.5 mm. This sheet was heated at 110 ° C. and stretched 5 times in the film flow direction (longitudinal direction). The sheet stretched 5 times was heated at 160 ° C. and stretched 10 times in the direction perpendicular to the flow direction (lateral direction), the thickness of the base layer: 38.5 μm, the thickness of the surface layer: 0.5 μm, A biaxially oriented polypropylene multilayer film having a thickness of the back layer: 0.5 μm (total film thickness: 37.2 μm) was obtained. The surface layer and the back surface layer of the biaxially oriented polypropylene multilayer film were subjected to corona treatment. The physical properties of the biaxially stretched multilayer polypropylene film were measured by the method described above. The evaluation results are shown in Table 1.
〔比較例２〕
＜基材層：プロピレン重合体組成物層＞
前記ＰＰ−１、ＰＰ−２、ＰＰ−１に予め炭酸カルシウムを混練した組成物およびＰＰ−１に予め酸化チタンを混練した組成物を用意し、当該成分をドライブレンドして、ＰＰ−１を６４．２質量％、ＰＰ−２を２１．４質量％、炭酸カルシウムを１２．１質量％、および酸化チタンを２．２質量％含む基材層用プロピレン重合体組成物を用意した。
[Comparative Example 2]
<Base material layer: Propylene polymer composition layer>
A composition in which calcium carbonate is previously kneaded with PP-1, PP-2, PP-1 and a composition in which titanium oxide is kneaded in advance with PP-1 are prepared. A propylene polymer composition for a base layer containing 64.2% by mass, 21.4% by mass of PP-2, 12.1% by mass of calcium carbonate, and 2.2% by mass of titanium oxide was prepared.
＜表面層：プロピレン系重合体層＞
前記ＰＰ−２およびＰＰ−３をドライブレンドして、ＰＰ−２を５０質量％、およびＰＰ−３を５０質量％含む表面層用プロピレン系重合体組成物を用意した。
<Surface layer: Propylene polymer layer>
The PP-2 and PP-3 were dry blended to prepare a propylene polymer composition for a surface layer containing 50% by mass of PP-2 and 50% by mass of PP-3.
＜裏面層：プロピレン系重合体層＞
前記ＰＰ−１およびＰＰ−２をドライブレンドして、ＰＰ−１を３０質量％、およびＰＰ−２を７０質量％含む裏面層用プロピレン系重合体組成物を用意した。
<Back layer: Propylene polymer layer>
The PP-1 and PP-2 were dry blended to prepare a propylene polymer composition for the back layer containing 30% by mass of PP-1 and 70% by mass of PP-2.
＜二軸延伸多層ポリプロピレンフィルムの製造＞
前記表面層用プロピレン系重合体組成物、基材層用プロピレン重合体組成物及び裏面層用プロピレン系重合体組成物を押出量比（表面層／基材層／裏面層：９．１／２２．６／１）になるよう各々スクリュー押出機を用いて溶融押出し、マルチマニホールドタイプＴ−ダイから押出後、冷却ロール上にて急冷し厚さ約１．０ｍｍの多層シートを得た。このシートを１１０℃で加熱しフィルムの流れ方向（縦方向）に５倍延伸した。この５倍延伸したシートを１６０℃で加熱し流れ方向に対して直交する方向（横方向）に１０倍延伸して、基層の厚さ：１８．３μｍ、表面層の厚さ：４．３μｍ、裏面層の厚さ：０．５μｍ（合計フィルム厚さ：２３．１μｍ）の二軸延伸ポリプロピレン多層フィルムを得た。二軸延伸ポリプロピレン多層フィルムの表面層、裏面層には、コロナ処理を施した。かかる二軸延伸多層ポリプロピレンフィルムの物性等を前記記載の方法で測定した。評価結果を表１に示す。
<Manufacture of biaxially oriented multilayer polypropylene film>
The extrusion ratio of the propylene polymer composition for the surface layer, the propylene polymer composition for the substrate layer, and the propylene polymer composition for the back layer (surface layer / substrate layer / back layer: 9.1 / 22) .6 / 1) were each melt extruded using a screw extruder, extruded from a multi-manifold type T-die, and then rapidly cooled on a cooling roll to obtain a multilayer sheet having a thickness of about 1.0 mm. This sheet was heated at 110 ° C. and stretched 5 times in the film flow direction (longitudinal direction). The sheet stretched 5 times was heated at 160 ° C. and stretched 10 times in the direction perpendicular to the flow direction (lateral direction). The thickness of the base layer: 18.3 μm, the thickness of the surface layer: 4.3 μm, A biaxially oriented polypropylene multilayer film having a thickness of the back surface layer of 0.5 μm (total film thickness: 23.1 μm) was obtained. The surface layer and the back surface layer of the biaxially oriented polypropylene multilayer film were subjected to corona treatment. The physical properties of the biaxially stretched multilayer polypropylene film were measured by the method described above. The evaluation results are shown in Table 1.
本発明の二軸延伸多層ポリプロピレンフィルムは、低密度で且つ隠蔽性、酸素バリア性およびラミネート適性に優れており、かかる特徴を活かして、食品等の包装材料、なかでもガスバリア性が要求される内容物の食品包装材料を始め、トイレタリー製品の包装材料に好適に使用できる。 The biaxially stretched multilayer polypropylene film of the present invention has a low density and is excellent in concealability, oxygen barrier properties and laminate suitability. Utilizing such characteristics, contents that require gas barrier properties such as food packaging materials. It can be suitably used as a packaging material for toiletry products as well as food packaging materials.
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| CN111164138A (en) * | 2017-09-29 | 2020-05-15 | 陶氏环球技术有限责任公司 | Partially coated film and package formed therefrom |
| JP2021160723A (en) * | 2020-03-30 | 2021-10-11 | 福岡県 | Fruit and vegetable freshness preservation film for automatic packaging and fruit and vegetable freshness preservation packaging bag |
| JP7324959B1 (en) * | 2023-05-18 | 2023-08-10 | 株式会社Tbm | LAMINATED SHEET AND FOOD PACKAGING CONTAINER |
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