JP6901058B1 - Paper laminate - Google Patents
Paper laminate Download PDFInfo
- Publication number
- JP6901058B1 JP6901058B1 JP2021514141A JP2021514141A JP6901058B1 JP 6901058 B1 JP6901058 B1 JP 6901058B1 JP 2021514141 A JP2021514141 A JP 2021514141A JP 2021514141 A JP2021514141 A JP 2021514141A JP 6901058 B1 JP6901058 B1 JP 6901058B1
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- JP
- Japan
- Prior art keywords
- paper
- mass
- resin layer
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- paper laminate
- Prior art date
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- 239000011101 paper laminate Substances 0.000 title claims abstract description 106
- 229920005989 resin Polymers 0.000 claims abstract description 152
- 239000011347 resin Substances 0.000 claims abstract description 152
- 239000010410 layer Substances 0.000 claims abstract description 150
- 239000000123 paper Substances 0.000 claims abstract description 144
- 239000011241 protective layer Substances 0.000 claims abstract description 79
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 65
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 63
- 239000000758 substrate Substances 0.000 claims abstract description 30
- 125000002091 cationic group Chemical group 0.000 claims abstract description 26
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims description 90
- 229920001577 copolymer Polymers 0.000 claims description 37
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 29
- 239000007787 solid Substances 0.000 claims description 23
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 21
- 150000001336 alkenes Chemical class 0.000 claims description 21
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 21
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 18
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 18
- 239000000565 sealant Substances 0.000 claims description 16
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 11
- 239000005995 Aluminium silicate Substances 0.000 claims description 10
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 claims description 10
- 235000012211 aluminium silicate Nutrition 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 6
- 239000000440 bentonite Substances 0.000 claims description 4
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- 238000004806 packaging method and process Methods 0.000 claims description 3
- 230000004888 barrier function Effects 0.000 abstract description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 49
- 239000002655 kraft paper Substances 0.000 description 44
- 238000000576 coating method Methods 0.000 description 20
- 239000007789 gas Substances 0.000 description 20
- 239000000178 monomer Substances 0.000 description 20
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- 238000010494 dissociation reaction Methods 0.000 description 19
- 230000005593 dissociations Effects 0.000 description 19
- 238000001035 drying Methods 0.000 description 17
- 239000003973 paint Substances 0.000 description 16
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 15
- -1 alkyl ketene dimer Chemical compound 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000006185 dispersion Substances 0.000 description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 11
- 239000005977 Ethylene Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
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- 230000005540 biological transmission Effects 0.000 description 8
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
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- 229920000768 polyamine Polymers 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 6
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- 239000000057 synthetic resin Substances 0.000 description 6
- 229920002873 Polyethylenimine Polymers 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
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- 238000006482 condensation reaction Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 229920001131 Pulp (paper) Polymers 0.000 description 4
- 229920006243 acrylic copolymer Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011121 hardwood Substances 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
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- UTOVMEACOLCUCK-SNAWJCMRSA-N (e)-4-butoxy-4-oxobut-2-enoic acid Chemical compound CCCCOC(=O)\C=C\C(O)=O UTOVMEACOLCUCK-SNAWJCMRSA-N 0.000 description 2
- IZUVGRMMRWJVKU-UHFFFAOYSA-N 3-ethoxycarbonylbut-3-enoic acid Chemical compound CCOC(=O)C(=C)CC(O)=O IZUVGRMMRWJVKU-UHFFFAOYSA-N 0.000 description 2
- WHBMMWSBFZVSSR-UHFFFAOYSA-N 3-hydroxybutyric acid Chemical compound CC(O)CC(O)=O WHBMMWSBFZVSSR-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229920006167 biodegradable resin Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004061 bleaching Methods 0.000 description 2
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 2
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 2
- 238000010227 cup method (microbiological evaluation) Methods 0.000 description 2
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- 239000000975 dye Substances 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
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- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
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- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
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- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/62—Macromolecular organic compounds or oligomers thereof obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/80—Paper comprising more than one coating
- D21H19/82—Paper comprising more than one coating superposed
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Paper (AREA)
- Laminated Bodies (AREA)
- Wrappers (AREA)
Abstract
本発明は、離解性に優れ、高いバリア性を有する紙積層体を提供することを主な目的とする。本発明の紙積層体は、紙基材と、紙基材の少なくとも一方の面に樹脂層および保護層と、を有する紙積層体であって、紙基材の密度が０．５０ｇ／ｃｍ３以上０．９０ｇ／ｃｍ３以下であり、紙基材の片方の面が平滑面であり、ＪＩＳ Ｐ ８１５５：２０１０に準拠して測定される、平滑面の王研式平滑度が１００秒以上であり、樹脂層が水懸濁性高分子、アスペクト比が５０以上の板状無機化合物、およびカチオン性樹脂を含有し、保護層が水溶性高分子を含有する。An object of the present invention is to provide a paper laminate having excellent disintegration property and high barrier property. The paper laminate of the present invention is a paper laminate having a paper substrate and a resin layer and a protective layer on at least one surface of the paper substrate, and the density of the paper substrate is 0.50 g / cm3 or more. It is 0.90 g / cm3 or less, one surface of the paper substrate is a smooth surface, and the smooth surface measured according to JIS P 8155: 2010 has a smooth surface of 100 seconds or more. The resin layer contains a water-suspendable polymer, a plate-like inorganic compound having an aspect ratio of 50 or more, and a cationic resin, and the protective layer contains a water-soluble polymer.
Description
本発明は、紙積層体に関する。 The present invention relates to a paper laminate.
紙基材に水蒸気バリア性やガスバリア性（とくに、酸素バリア性）を付与した包装材料は、食品、医療品、電子部品等の包装において、内容物の品質低下を防止するために、従来から用いられている。 Packaging materials that have water vapor barrier properties and gas barrier properties (particularly oxygen barrier properties) added to the paper base material have been conventionally used in packaging foods, medical products, electronic parts, etc. in order to prevent deterioration of the quality of the contents. Has been done.
紙基材に水蒸気バリア性やガスバリア性を付与する方法としては、水蒸気バリア性やガスバリア性に優れた合成樹脂フィルムを紙基材に積層する方法が一般的である。しかし、紙基材に合成樹脂フィルム等を積層した材料は、使用後に紙や合成樹脂等をリサイクルすることが困難であり、環境面において課題を有するものであった。 As a method for imparting water vapor barrier property or gas barrier property to a paper base material, a method of laminating a synthetic resin film having excellent water vapor barrier property or gas barrier property on the paper base material is common. However, it is difficult to recycle paper, synthetic resin, etc. after use of a material in which a synthetic resin film or the like is laminated on a paper base material, which poses an environmental problem.
そこで、合成樹脂フィルム等を使用せずに、紙を基材としたバリア性材料の開発が進められてきている。たとえば、特許文献１には、紙基材上に、水蒸気バリア層、ガスバリア層がこの順で設けられた紙製バリア材料が提案されている。前記水蒸気バリア層は、水蒸気バリア性樹脂および撥水剤を含有し、かつ前記ガスバリア層は、水溶性高分子および界面活性剤を含有する。
また、特許文献２には、紙基材上に水蒸気バリア層およびガスバリア層が設けられた紙製バリア包装材料が提案されている。水蒸気バリア層は、平均粒子径５μｍ以上、アスペクト比１０以上のカオリンを全顔料に対して５０〜１００重量％含有し、ガスバリア層のバインダー樹脂は、ポリビニルアルコール樹脂である。Therefore, the development of a barrier material based on paper has been promoted without using a synthetic resin film or the like. For example, Patent Document 1 proposes a paper barrier material in which a water vapor barrier layer and a gas barrier layer are provided in this order on a paper base material. The water vapor barrier layer contains a water vapor barrier resin and a water repellent, and the gas barrier layer contains a water-soluble polymer and a surfactant.
Further, Patent Document 2 proposes a paper barrier packaging material in which a water vapor barrier layer and a gas barrier layer are provided on a paper base material. The water vapor barrier layer contains 50 to 100% by weight of kaolin having an average particle size of 5 μm or more and an aspect ratio of 10 or more with respect to all pigments, and the binder resin of the gas barrier layer is a polyvinyl alcohol resin.
特許文献１および２のように、紙基材のガスバリア性および水蒸気バリア性を向上させる試みはなされているものの、十分なバリア性が得られていない。また、一般的に、カレンダーを用いて平滑処理を施された原紙では、平滑化に際して原紙にかかる圧力が高く、原紙の通気性と透湿性が低下し、紙基材の離解性が損なわれてリサイクル性が低下する。このように、相反する関係にあるバリア性とリサイクル性とを両立させるには、必ずしも満足すべき結果が得られていないのが現状である。
そこで、本発明は、離解性に優れ、高いバリア性を有する紙積層体を提供することを主な目的とする。Although attempts have been made to improve the gas barrier property and the water vapor barrier property of the paper base material as in Patent Documents 1 and 2, sufficient barrier properties have not been obtained. Further, in general, in a base paper that has been smoothed using a calendar, the pressure applied to the base paper during smoothing is high, the air permeability and moisture permeability of the base paper are lowered, and the disintegration property of the paper base material is impaired. Recyclability is reduced. As described above, in order to achieve both barrier properties and recyclability, which are in a contradictory relationship, the current situation is that satisfactory results are not always obtained.
Therefore, an object of the present invention is to provide a paper laminate having excellent disintegration property and high barrier property.
本発明者等は、鋭意検討の結果、特定の紙基材に、樹脂層と保護層とを備え、樹脂層が水懸濁性高分子、特定のアスペクト比を有する板状無機化合物、およびカチオン性樹脂を含有し、保護層が水溶性高分子を含有する紙積層体が、前記課題を解決することを見出した。
すなわち、本発明は、下記の紙積層体に係る。
＜１＞：紙基材と、前記紙基材の少なくとも一方の面に樹脂層および保護層と、を有する紙積層体であって、前記紙基材の密度が０．５０ｇ／ｃｍ３以上０．９０ｇ／ｃｍ３以下であり、前記紙基材の片方の面が平滑面であり、ＪＩＳ Ｐ ８１５５：２０１０に準拠して測定される、前記平滑面の王研式平滑度が１００秒以上であり、前記樹脂層が水懸濁性高分子、アスペクト比が５０以上の板状無機化合物、およびカチオン性樹脂を含有し、前記保護層が水溶性高分子を含有する、紙積層体。
＜２＞：前記平滑面の逆側の面に前記樹脂層と前記保護層とを有する、＜１＞に記載の紙積層体。
＜３＞：前記樹脂層中に含有される前記水懸濁性高分子が、オレフィン・不飽和カルボン酸系共重合体、スチレン・ブタジエン系共重合体およびスチレン・アクリル系共重体よりなる群から選ばれる１種以上を含む、＜１＞または＜２＞に記載の紙積層体。
＜４＞：前記樹脂層中に含有される前記板状無機化合物が、合成マイカ、ベントナイトおよびカオリンよりなる群から選ばれる１種以上を含む、＜１＞〜＜３＞のいずれかに記載の紙積層体。
＜５＞：前記樹脂層中に含有される前記板状無機化合物の含有量が、前記水懸濁性高分子１００質量部に対して０．１質量部以上８００質量部以下である、＜１＞〜＜４＞のいずれかに記載の紙積層体。
＜６＞：前記樹脂層中に含有される前記板状無機化合物の厚さが、２００ｎｍ以下である、＜１＞〜＜５＞のいずれかに記載の紙積層体。
＜７＞：前記樹脂層中に含有される前記板状無機化合物の含有割合が、前記樹脂層の全固形量中０．１質量％以上８０質量％以下である、＜１＞〜＜６＞のいずれかに記載の紙積層体。
＜８＞：前記保護層中に含有される前記水溶性高分子が、ポリビニルアルコールおよび変性ポリビニルアルコールよりなる群から選ばれる１種以上を含む、＜１＞〜＜７＞のいずれかに記載の紙積層体。
＜９＞：前記紙基材の坪量が、２０ｇ／ｍ２以上１００ｇ／ｍ２以下である、＜１＞〜＜８＞のいずれかに記載の紙積層体。
＜１０＞：前記紙基材は、ＪＩＳ Ｐ ８１５５：２０１０に準拠して測定される、前記平滑面の逆側の面の王研式平滑度が１００秒未満である、＜１＞〜＜９＞のいずれかに記載の紙積層体。
＜１１＞：前記樹脂層中に含有される前記カチオン性樹脂の含有量は、前記板状無機化合物１００質量部に対して、０．５質量部以上３００質量部以下である、＜１＞〜＜１０＞のいずれかに記載の紙積層体。
＜１２＞：前記樹脂層中に含有される前記カチオン性樹脂の含有量は、前記水懸濁性高分子１００質量部に対して、０．１質量部以上１００質量部以下である、＜１＞〜＜１１＞のいずれかに記載の紙積層体。
＜１３＞：少なくとも一方の最外層にシーラント層をさらに有する、＜１＞〜＜１２＞のいずれかに記載の紙積層体。
＜１４＞：包装用材料である、＜１＞〜＜１３＞のいずれかに記載の紙積層体。As a result of diligent studies, the present inventors have provided a resin layer and a protective layer on a specific paper substrate, and the resin layer is a water-suspendable polymer, a plate-like inorganic compound having a specific aspect ratio, and a cation. It has been found that a paper laminate containing a sex resin and a protective layer containing a water-soluble polymer solves the above-mentioned problems.
That is, the present invention relates to the following paper laminate.
<1>: A paper laminate having a paper base material and a resin layer and a protective layer on at least one surface of the paper base material, and the density of the paper base material is 0.50 g / cm 3 or more and 0. .90 g / cm 3 or less, one side of the paper substrate is a smooth surface, and the smooth surface is measured in accordance with JIS P 8155: 2010, and the smoothness of the smooth surface is 100 seconds or more. A paper laminate in which the resin layer contains a water-suspendable polymer, a plate-like inorganic compound having an aspect ratio of 50 or more, and a cationic resin, and the protective layer contains a water-soluble polymer.
<2>: The paper laminate according to <1>, which has the resin layer and the protective layer on the surface opposite to the smooth surface.
<3>: The water-suspendable polymer contained in the resin layer is composed of an olefin / unsaturated carboxylic acid-based copolymer, a styrene / butadiene-based copolymer, and a styrene / acrylic-based copolymer. The paper laminate according to <1> or <2>, which comprises one or more selected types.
<4>: The method according to any one of <1> to <3>, wherein the plate-like inorganic compound contained in the resin layer contains at least one selected from the group consisting of synthetic mica, bentonite and kaolin. Paper laminate.
<5>: The content of the plate-like inorganic compound contained in the resin layer is 0.1 part by mass or more and 800 parts by mass or less with respect to 100 parts by mass of the water-suspending polymer, <1. > To the paper laminate according to any one of <4>.
<6>: The paper laminate according to any one of <1> to <5>, wherein the thickness of the plate-like inorganic compound contained in the resin layer is 200 nm or less.
<7>: The content ratio of the plate-like inorganic compound contained in the resin layer is 0.1% by mass or more and 80% by mass or less in the total solid content of the resin layer, <1> to <6>. The paper laminate according to any one of.
<8>: The method according to any one of <1> to <7>, wherein the water-soluble polymer contained in the protective layer contains at least one selected from the group consisting of polyvinyl alcohol and modified polyvinyl alcohol. Paper laminate.
<9>: The paper laminate according to any one of <1> to <8>, wherein the basis weight of the paper base material is 20 g / m 2 or more and 100 g / m 2 or less.
<10>: The paper substrate has a Wangken-type smoothness of the surface opposite to the smooth surface measured in accordance with JIS P 8155: 2010, which is less than 100 seconds, <1> to <9. > The paper laminate according to any one of.
<11>: The content of the cationic resin contained in the resin layer is 0.5 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the plate-shaped inorganic compound, <1> to The paper laminate according to any one of <10>.
<12>: The content of the cationic resin contained in the resin layer is 0.1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the water-suspended polymer, <1. > To <11>. The paper laminate according to any one of.
<13>: The paper laminate according to any one of <1> to <12>, which further has a sealant layer on at least one outermost layer.
<14>: The paper laminate according to any one of <1> to <13>, which is a packaging material.
本発明を実施するための形態（以下、単に「本実施形態」という。）について詳細に説明する。以下の本実施形態は、本発明を説明するための例示であり、本発明の内容に限定されるものではない。本発明は、その要旨の範囲内で適宜に変形して実施できる。本実施形態において、好ましいとされている規定は任意に採用することができ、好ましいもの同士の組み合わせはより好ましいといえる。 A mode for carrying out the present invention (hereinafter, simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not limited to the contents of the present invention. The present invention can be appropriately modified and implemented within the scope of the gist thereof. In the present embodiment, the preferred provisions can be arbitrarily adopted, and it can be said that the combination of preferable ones is more preferable.
＜紙積層体＞
本実施形態の紙積層体は、紙基材と、紙基材の少なくとも一方の面に樹脂層および保護層と、を有する紙積層体であって、紙基材の密度が０．５０ｇ／ｃｍ３以上０．９０ｇ／ｃｍ３以下であり、紙基材の片方の面が平滑面であり、ＪＩＳ Ｐ ８１５５：２０１０に準拠して測定される、平滑面の王研式平滑度が１００秒以上であり、樹脂層が水懸濁性高分子、アスペクト比が５０以上の板状無機化合物、およびカチオン性樹脂を含有し、保護層が水溶性高分子を含有する。
本実施形態の紙積層体は、離解性に優れ、高いバリア性を有する。
本実施形態において、王研式平滑度がもう一方の面より高い面を平滑面と呼び、王研式平滑度が低い面を非平滑面と呼ぶ。<Paper laminate>
The paper laminate of the present embodiment is a paper laminate having a paper substrate and a resin layer and a protective layer on at least one surface of the paper substrate, and the density of the paper substrate is 0.50 g / cm. 3 or more and 0.90 g / cm 3 or less, one side of the paper substrate is a smooth surface, and the smooth surface measured according to JIS P 8155: 2010 has a smooth surface of 100 seconds or more. The resin layer contains a water-suspendable polymer, a plate-like inorganic compound having an aspect ratio of 50 or more, and a cationic resin, and the protective layer contains a water-soluble polymer.
The paper laminate of the present embodiment has excellent dissociability and a high barrier property.
In the present embodiment, a surface having a higher Oken-type smoothness than the other surface is called a smooth surface, and a surface having a lower Oken-type smoothness is called a non-smooth surface.
上記の効果が得られる理由は定かではないが、以下の理由が考えられる。
上記紙基材は平滑面の王研式平滑度が上記下限値以上であり、密度が上記範囲内であることで、繊維の収縮が抑えられるため、離解性が高く、地合の良い紙となる。地合いが良いと塗料を塗工した際に、浸みこみのムラが少なく、均一性の高い塗膜が得られる。そのため、本実施形態の紙積層体は、離解性に優れ、高いバリア性が発揮されると考えられる。The reason why the above effect is obtained is not clear, but the following reasons can be considered.
When the smooth surface of the paper base material has an Oken-type smoothness of the above lower limit or more and the density is within the above range, the shrinkage of fibers is suppressed, so that the paper has high dissociation and has a good texture. Become. If the texture is good, when the paint is applied, there is little unevenness of penetration and a highly uniform coating film can be obtained. Therefore, it is considered that the paper laminate of the present embodiment is excellent in dissociation property and exhibits high barrier property.
本実施形態の紙積層体は、紙基材と、前記紙基材の少なくとも一方の面に樹脂層および保護層と、を有する。紙基材の片面に樹脂層と保護層を有していてもよく、両面に樹脂層と保護層を有していてもよい。生産効率の点からは、片面に樹脂層と保護層を有することが好ましい。本実施形態においては、片面のみに樹脂層と保護層とを有しても、十分なバリア性、とくに酸素バリア性を発現することができる。以下、単にバリア性と表現した場合、水蒸気バリア性またはガスバリア性（とくに酸素バリア性）を指す。 The paper laminate of the present embodiment has a paper base material and a resin layer and a protective layer on at least one surface of the paper base material. The paper base material may have a resin layer and a protective layer on one side, or may have a resin layer and a protective layer on both sides. From the viewpoint of production efficiency, it is preferable to have a resin layer and a protective layer on one side. In the present embodiment, even if the resin layer and the protective layer are provided on only one side, sufficient barrier properties, particularly oxygen barrier properties, can be exhibited. Hereinafter, when simply expressed as a barrier property, it refers to a water vapor barrier property or a gas barrier property (particularly an oxygen barrier property).
本実施形態では、紙基材の片方の面が平滑面である。このとき、紙基材のもう片方の面が平滑面の逆側の面である。紙基材の樹脂層および保護層が設けられる面は、平滑面であってもよく、平滑面の逆側の面であってもよい。本実施形態では、平滑面の逆側の面に樹脂層と保護層とを有することが好ましい。これにより、紙基材が有する平滑面のバリア性と印刷適性をより効果的に発現させることができる。 In this embodiment, one surface of the paper substrate is a smooth surface. At this time, the other surface of the paper base material is the surface opposite to the smooth surface. The surface on which the resin layer and the protective layer of the paper base material are provided may be a smooth surface or a surface opposite to the smooth surface. In the present embodiment, it is preferable to have a resin layer and a protective layer on the surface opposite to the smooth surface. Thereby, the barrier property and printability of the smooth surface of the paper base material can be more effectively exhibited.
本実施形態では、紙基材の少なくとも一方の面に、紙基材に近い側から樹脂層と保護層とをこの順に有していてもよく、紙基材に近い側から保護層と樹脂層とをこの順に有していてもよい。本実施形態では、紙基材の少なくとも一方の面に、紙基材に近い側から、樹脂層と保護層とをこの順に有することが好ましい。
また、保護層が樹脂層上に直接形成されていることが好ましい。保護層が樹脂層上に直接形成されていることで、樹脂層が紙基材側と保護層側の両方からの機械的離解作用により水中で分散しやすく、本実施形態における紙基材の効果をより遺憾なく発揮させることができる。
さらに、本実施形態の紙積層体は、樹脂層が紙基材上に直接形成されていることが好ましい。樹脂層が紙基材上に直接形成されていることで、樹脂層と紙基材との密着性を高めることができ、紙積層体のバリア性をより向上させることができる。In the present embodiment, the resin layer and the protective layer may be provided in this order from the side closer to the paper base material on at least one surface of the paper base material, and the protective layer and the resin layer may be provided from the side closer to the paper base material. And may have in this order. In the present embodiment, it is preferable to have the resin layer and the protective layer in this order on at least one surface of the paper base material from the side closer to the paper base material.
Further, it is preferable that the protective layer is directly formed on the resin layer. Since the protective layer is directly formed on the resin layer, the resin layer is easily dispersed in water by the mechanical dissociation action from both the paper base material side and the protective layer side, and the effect of the paper base material in the present embodiment. Can be demonstrated more regretfully.
Further, in the paper laminate of the present embodiment, it is preferable that the resin layer is directly formed on the paper base material. Since the resin layer is directly formed on the paper base material, the adhesion between the resin layer and the paper base material can be enhanced, and the barrier property of the paper laminate can be further improved.
本実施形態の紙積層体において、水蒸気バリア性をより向上させる観点から、ＪＩＳ Ｚ ０２０８：１９７６（カップ法）Ｂ法（温度４０℃±０．５℃、相対湿度９０％±２％）に準拠して、紙積層体の樹脂層が内側（低湿度側）に来るように配置して測定される、本実施形態の紙積層体の水蒸気透過度は、好ましくは２０．０ｇ／（ｍ２・ｄａｙ）以下、より好ましくは１６．０ｇ／（ｍ２・ｄａｙ）以下、さらに好ましくは１２．０ｇ／（ｍ２・ｄａｙ）以下、さらに好ましくは１０．０ｇ／（ｍ２・ｄａｙ）以下、さらに好ましくは５．０ｇ／（ｍ２・ｄａｙ）以下である。本実施形態の紙積層体の水蒸気透過度は低ければ低いほど好ましいため下限値はとくに限定されないが、たとえば０．０１ｇ／（ｍ２・ｄａｙ）以上である。The paper laminate of the present embodiment conforms to JIS Z 0208: 1976 (cup method) B method (temperature 40 ° C. ± 0.5 ° C., relative humidity 90% ± 2%) from the viewpoint of further improving the water vapor barrier property. The water vapor transmission rate of the paper laminate of the present embodiment, which is measured by arranging the resin layer of the paper laminate so as to come to the inside (low humidity side), is preferably 20.0 g / (m 2 ·. day) or less, more preferably 16.0g / (m 2 · day) or less, more preferably 12.0g / (m 2 · day) or less, more preferably 10.0g / (m 2 · day) or less, further It is preferably 5.0 g / (m 2 · day) or less. The lower the water vapor transmission rate of the paper laminate of the present embodiment is, the more preferable it is. Therefore, the lower limit is not particularly limited, but is, for example, 0.01 g / (m 2 · day) or more.
本実施形態の紙積層体において、大気圧下で温度２３℃、相対湿度５０％の条件にて測定される、本実施形態の紙積層体の酸素透過度は、ガスバリア性をより向上させる観点から、好ましくは１０．０ｃｃ／（ｍ２・ｄａｙ・ａｔｍ）以下、より好ましくは５．０ｃｃ／（ｍ２・ｄａｙ・ａｔｍ）以下、さらに好ましくは２．０ｃｃ／（ｍ２・ｄａｙ・ａｔｍ）以下、さらに好ましくは１．０ｃｃ／（ｍ２・ｄａｙ・ａｔｍ）以下ある。本実施形態の紙積層体の酸素透過度は低ければ低いほど好ましいため下限値はとくに限定されないが、たとえば０．０１ｃｃ／（ｍ２・ｄａｙ・ａｔｍ）以上である。In the paper laminate of the present embodiment, the oxygen permeability of the paper laminate of the present embodiment measured under the conditions of a temperature of 23 ° C. and a relative humidity of 50% under atmospheric pressure is from the viewpoint of further improving the gas barrier property. , Preferably 10.0 cc / (m 2 · day · atm) or less, more preferably 5.0 cc / (m 2 · day · atm) or less, still more preferably 2.0 cc / (m 2 · day · atm) or less. , even more preferably 1.0cc / (m 2 · day · atm) or less. The lower limit for the oxygen permeability of the paper stack is preferably as low as possible in the present embodiment is not limited particularly, but for example 0.01cc / (m 2 · day · atm) or more.
本実施形態の紙積層体の離解率は、紙基材として晒クラフト紙を用いた場合、離解性をより向上させる観点から、好ましくは９２．５％以上、より好ましくは９３．０％以上、さらに好ましくは９４．０％以上、さらに好ましくは９５．０％以上、さらに好ましくは９６．０％以上であり、そして、たとえば１００％以下である。
本実施形態の紙積層体の離解率は、紙基材として未晒クラフト紙を用いた場合、離解性をより向上させる観点から、好ましくは８７．０％以上、より好ましくは８８．０％以上、さらに好ましくは８８．５％以上、さらに好ましくは８９．０％以上であり、そして、たとえば１００％以下である。
離解率は、本実施形態の紙積層体をＪＩＳ Ｐ ８２２０：２０１２に準拠して離解し、離解開始から１０分後にスクリーン上の試料を回収して乾燥させることで残渣の質量比率（％）を算出し、１００−残渣の質量比率により算出される。When bleached kraft paper is used as the paper base material, the disintegration rate of the paper laminate of the present embodiment is preferably 92.5% or more, more preferably 93.0% or more, from the viewpoint of further improving the disintegration property. It is more preferably 94.0% or more, still more preferably 95.0% or more, still more preferably 96.0% or more, and for example 100% or less.
When unbleached kraft paper is used as the paper base material, the dissociation rate of the paper laminate of the present embodiment is preferably 87.0% or more, more preferably 88.0% or more from the viewpoint of further improving the dissociation property. , More preferably 88.5% or more, even more preferably 89.0% or more, and for example 100% or less.
The disintegration rate is determined by dissociating the paper laminate of the present embodiment in accordance with JIS P 8220: 2012, and collecting and drying the sample on the screen 10 minutes after the start of disaggregation to determine the mass ratio (%) of the residue. Calculated and calculated by the mass ratio of 100-residue.
［紙基材］
本実施形態における紙基材は、密度が０．５０ｇ／ｃｍ３以上０．９０ｇ／ｃｍ３以下であり、包装用紙として使用する観点から、好ましくは０．７０ｇ／ｃｍ３以上、より好ましくは０．７３ｇ／ｃｍ３以上であり、そして離解性をより向上させる観点から、好ましくは０．８５ｇ／ｃｍ３以下、より好ましくは０．８３ｇ／ｃｍ３以下である。密度は、ＪＩＳ Ｐ ８１１８：１９９８に準拠して測定される値である。[Paper base material]
The paper substrate in the present embodiment has a density of 0.50 g / cm 3 or more and 0.90 g / cm 3 or less, and is preferably 0.70 g / cm 3 or more, more preferably 0, from the viewpoint of being used as wrapping paper. It is .73 g / cm 3 or more, and is preferably 0.85 g / cm 3 or less, more preferably 0.83 g / cm 3 or less, from the viewpoint of further improving the disintegration property. Density is a value measured according to JIS P 8118: 1998.
本実施形態における紙基材は、片方の面が平滑面であり、平滑面の王研式平滑度が１００秒以上である。平滑面の王研式平滑度は、紙積層体の離解性およびバリア性をより向上させる観点から、２００秒以上が好ましく、２５０秒以上が好ましく、３００秒以上がより好ましく、３５０秒以上がさらに好ましく、４００秒以上がさらに好ましい。一方、平滑面の王研式平滑度は、紙積層体のバリア性、地合いおよび不透明度をより向上させる観点から、１０００秒以下が好ましく、８００秒以下がより好ましく、６００秒以下がさらに好ましく、５００秒以下がさらに好ましく、４５０秒以下がさらに好ましい。かかる平滑面の逆側の面は、王研式平滑度が平滑面よりも小さければよく、とくに限定されないが、好ましくは１秒以上、より好ましくは１０秒以上であり、そして好ましくは１００秒より小さく、より好ましくは９０秒以下、さらに好ましくは５０秒以下である。王研式平滑度は、ＪＩＳ Ｐ ８１５５：２０１０に準拠して測定される値である。 One surface of the paper substrate in the present embodiment is a smooth surface, and the smooth surface has a smoothness of 100 seconds or more. The Oken-type smoothness of the smooth surface is preferably 200 seconds or longer, preferably 250 seconds or longer, more preferably 300 seconds or longer, further preferably 350 seconds or longer, from the viewpoint of further improving the dissociation property and barrier property of the paper laminate. It is preferable, and 400 seconds or more is more preferable. On the other hand, the Oken-type smoothness of the smooth surface is preferably 1000 seconds or less, more preferably 800 seconds or less, further preferably 600 seconds or less, from the viewpoint of further improving the barrier property, texture and opacity of the paper laminate. More preferably 500 seconds or less, and even more preferably 450 seconds or less. The surface opposite to the smooth surface may have a Wangken-type smoothness smaller than that of the smooth surface, and is not particularly limited, but is preferably 1 second or longer, more preferably 10 seconds or longer, and preferably 100 seconds or longer. It is small, more preferably 90 seconds or less, still more preferably 50 seconds or less. The Oken-type smoothness is a value measured in accordance with JIS P 8155: 2010.
紙基材を構成するパルプとしては、たとえば、木材パルプ、非木材パルプ等が挙げられる。
木材パルプとしては、たとえば、針葉樹パルプ、広葉樹パルプ等が挙げられる。
紙基材の通気性と透湿性を高めて離解性を向上する観点から、紙基材を構成するパルプ全体の４０質量％以上を広葉樹パルプとすることが好ましく、５０質量％以上を広葉樹パルプとすることがより好ましい。また、広葉樹パルプの使用量の上限値は、たとえば、紙基材を構成するパルプ全体の１００質量％以下、好ましくは９５質量％以下、より好ましくは９０質量％以下である。
一方、針葉樹パルプの繊維が長いため、紙基材の引張強度を高める観点から、紙基材を構成するパルプ全体の５質量％以上を針葉樹パルプとすることが好ましく、１０質量％以上とすることがより好ましい。また、針葉樹パルプの使用量の上限値は、たとえば、紙基材を構成するパルプ全体の６０質量％以下、好ましくは５０質量％以下である。Examples of the pulp constituting the paper base material include wood pulp and non-wood pulp.
Examples of wood pulp include softwood pulp and hardwood pulp.
From the viewpoint of improving the air permeability and moisture permeability of the paper base material to improve the disintegration property, it is preferable that 40% by mass or more of the total pulp constituting the paper base material is hardwood pulp, and 50% by mass or more is hardwood pulp. It is more preferable to do so. The upper limit of the amount of hardwood pulp used is, for example, 100% by mass or less, preferably 95% by mass or less, and more preferably 90% by mass or less of the total pulp constituting the paper base material.
On the other hand, since the fibers of softwood pulp are long, from the viewpoint of increasing the tensile strength of the paper base material, it is preferable that 5% by mass or more of the total pulp constituting the paper base material is softwood pulp, and 10% by mass or more. Is more preferable. The upper limit of the amount of softwood pulp used is, for example, 60% by mass or less, preferably 50% by mass or less of the total pulp constituting the paper base material.
非木材パルプとしては、たとえば、綿パルプ、麻パルプ、ケナフパルプ、竹パルプ等が挙げられる。レーヨン繊維やナイロン繊維等の合成繊維等のパルプ繊維以外の材料を、本発明の効果を損なわない限り、副資材として配合してもよい。 Examples of non-wood pulp include cotton pulp, hemp pulp, kenaf pulp, bamboo pulp and the like. Materials other than pulp fibers such as synthetic fibers such as rayon fibers and nylon fibers may be blended as auxiliary materials as long as the effects of the present invention are not impaired.
紙基材は、たとえば、パルプスラリーを主成分とする抄紙原料を抄紙することにより得られる。
パルプスラリーは、木材または非木材の原料チップから、蒸解、洗浄、漂白等の工程を経て得られる。蒸解方法、洗浄方法、漂白方法等にとくに限定はない。これらの工程を経て得られたパルプスラリーは、さらに、水の存在下で叩解される。The paper substrate can be obtained, for example, by making a papermaking material containing pulp slurry as a main component.
Pulp slurries are obtained from wood or non-wood raw material chips through steps such as cooking, washing and bleaching. The cooking method, washing method, bleaching method, etc. are not particularly limited. The pulp slurry obtained through these steps is further beaten in the presence of water.
パルプのフリーネス（濾水度）は、とくに限定されず、好ましくは１５０ｍＬＣＳＦ以上、より好ましくは２５０ｍＬＣＳＦ以上であり、そして好ましくは６００ｍＬＣＳＦ以下、より好ましくは５００ｍＬＣＳＦ以下である。フリーネスを調節することによって、所望とする密度を好適に調整することができる。すなわち、フリーネスを１５０ｍＬＣＳＦ以上とすることによって、紙基材の密度を下げて、通気性と透湿性を高めることができる。一方、フリーネスを６００ｍＬＣＳＦ以下とすることによって、紙基材の密度を上げて、平滑面のバリア性を高めることができる。ここで、フリーネスとは、ＪＩＳ Ｐ８１２１−２：２０１２によるカナダ標準ろ水度のことである。フリーネスを調節するために、パルプを叩解する方法については、公知の方法を使用することができる。 The freeness of the pulp is not particularly limited, and is preferably 150 mL CSF or more, more preferably 250 mL CSF or more, and preferably 600 mL CSF or less, more preferably 500 mL CSF or less. By adjusting the freeness, the desired density can be suitably adjusted. That is, by setting the freeness to 150 mL CSF or more, the density of the paper base material can be lowered and the air permeability and moisture permeability can be improved. On the other hand, by setting the freeness to 600 mL CSF or less, the density of the paper base material can be increased and the barrier property of the smooth surface can be enhanced. Here, freeness is the Canadian standard freeness according to JIS P8121-2: 2012. Known methods can be used for beating pulp to control freeness.
紙基材には、必要に応じて、填料を適宜添加してもよい。填料としては、カオリン、タルク、重質炭酸カルシウム、軽質炭酸カルシウム、亜硫酸カルシウム、石膏、焼成カオリン、ホワイトカーボン、非晶質シリカ、デラミネーテッドカオリン、珪藻土、炭酸マグネシウム、水酸化アルミニウム、水酸化カルシウム、水酸化マグネシウム、水酸化亜鉛、二酸化チタン等を例示することができる。 If necessary, a filler may be appropriately added to the paper substrate. Fillers include kaolin, talc, heavy calcium carbonate, light calcium carbonate, calcium sulfite, gypsum, calcined kaolin, white carbon, amorphous silica, delaminated kaolin, diatomaceous earth, magnesium carbonate, aluminum hydroxide, calcium hydroxide. , Magnesium hydroxide, zinc hydroxide, titanium dioxide and the like can be exemplified.
紙基材中にはパルプや填料の他に、たとえば、サイズ剤、紙力増強剤、歩留向上剤、濾水性向上剤、ｐＨ調整剤、柔軟剤、帯電防止剤、消泡剤等の公知の抄紙用内添剤を必要に応じて添加することができる。サイズ剤としては、たとえば、ロジン系、アルキルケテンダイマー系、アルケニル無水コハク酸系、スチレン−アクリル系、高級脂肪酸系、石油樹脂系サイズ剤等が挙げられる。 In addition to pulp and fillers, paper base materials include, for example, sizing agents, paper strength enhancers, yield improvers, drainage improvers, pH adjusters, fabric softeners, antistatic agents, defoamers, and the like. The internal additive for papermaking can be added as needed. Examples of the sizing agent include rosin-based, alkyl ketene dimer-based, alkenyl succinic anhydride-based, styrene-acrylic, higher fatty acid-based, and petroleum resin-based sizing agents.
紙基材の坪量は、とくに限定されないが、所望の密度や厚みを得る観点から、２０ｇ／ｍ２以上が好ましく、３０ｇ／ｍ２以上がより好ましく、４０ｇ／ｍ２以上がさらに好ましく、そして１００ｇ／ｍ２以下が好ましく、９０ｇ／ｍ２以下がより好ましく、８０ｇ／ｍ２以下がさらに好ましい。The basis weight of the paper substrate is not particularly limited, but from the viewpoint of obtaining a desired density and thickness, 20 g / m 2 or more is preferable, 30 g / m 2 or more is more preferable, 40 g / m 2 or more is further preferable, and 100 g / m 2 or less, and more preferably not more than 90g / m 2, 80g / m 2 or less is more preferred.
紙基材の抄紙においては、公知の湿式抄紙機、たとえば、長網抄紙機、ギャップフォーマー型抄紙機、円網式抄紙機、短網式抄紙機等の抄紙機を適宜選択して使用することができる。抄紙機によって形成された湿紙は、フェルトにて搬送され、ドライヤーで乾燥される。ドライヤー乾燥前にプレドライヤーとして、多段式シリンダードライヤーを使用してもよい。湿紙を半乾燥状態でオンマシンブレーカースタックにより平滑化処理を施してもよいし、乾燥状態でオンマシンまたはオフマシンカレンダーにより平滑化処理を施してもよい。 For paper-based paper making, a known wet paper machine, for example, a long net paper machine, a gap former type paper machine, a circular net type paper machine, a short net type paper machine, or the like is appropriately selected and used. be able to. The wet paper formed by the paper machine is conveyed by felt and dried by a dryer. A multi-stage cylinder dryer may be used as a pre-dryer before drying the dryer. The wet paper may be smoothed by an on-machine breaker stack in a semi-dry state, or may be smoothed by an on-machine or off-machine calendar in a dry state.
本実施形態における紙基材としては片艶紙が好ましい。片艶紙とは、ヤンキードライヤーに圧接して乾燥することによって得られる紙である。片艶紙は抄紙時にヤンキードライヤーなどに接しながら乾燥される（拘束乾燥）ことで、繊維の収縮が抑えられるため、離解性が高く、地合の良い紙となる。地合いが良いと塗料を塗工した際に、浸みこみのムラが少なく、均一性の高い塗膜が得られる。そのため、紙基材として片艶紙を用いると、離解性により優れ、より一層高いバリア性が発揮されると考えられる。
また、紙基材として片艶紙を使用することにより、平滑化に際して紙基材にかかる圧力が少ないため、より一層高い通気性と透湿性を有し、さらに樹脂層と保護層を設けても優れた離解性を発現し、リサイクル性を高めることができる。また、紙基材の片方の面が平滑面であって密度が高いことから、通気性と透湿性を有することとは相反するバリア性の向上に寄与することができる。
また、本実施形態における紙基材は、植物由来のパルプを主成分として一般的に用いられている紙であればとくに制限はない。本実施形態における紙基材としては、具体的には、晒または未晒クラフト紙、片艶紙、上質紙、板紙、ライナー紙、塗工紙、グラシン紙、グラファン紙等を挙げることができる。これらの中でも、片艶紙、晒または未晒クラフト紙が好ましく、離解性を向上させる観点からは晒クラフト紙、片艶紙、片艶晒クラフト紙が好ましく、不透明度を向上させる観点からは未晒クラフト紙、片艶未晒クラフト紙が好ましい。As the paper base material in this embodiment, single glossy paper is preferable. Single-glossy paper is paper obtained by pressing and drying it with a Yankee dryer. The single-gloss paper is dried while in contact with a Yankee dryer or the like during papermaking (restraint drying), so that the shrinkage of the fibers is suppressed, so that the paper has high dissociation and a good texture. If the texture is good, when the paint is applied, there is little unevenness of penetration and a highly uniform coating film can be obtained. Therefore, it is considered that when single-glossy paper is used as the paper base material, the dissociation property is excellent and the barrier property is further enhanced.
Further, by using single-gloss paper as the paper base material, the pressure applied to the paper base material during smoothing is small, so that the paper base material has even higher air permeability and moisture permeability, and even if a resin layer and a protective layer are provided. It can exhibit excellent dissociability and enhance recyclability. Further, since one surface of the paper base material is a smooth surface and has a high density, it can contribute to the improvement of the barrier property, which is contrary to having the air permeability and the moisture permeability.
Further, the paper base material in the present embodiment is not particularly limited as long as it is a paper generally used with plant-derived pulp as a main component. Specific examples of the paper base material in the present embodiment include bleached or unbleached kraft paper, single-gloss paper, high-quality paper, paperboard, liner paper, coated paper, glassin paper, and graphan paper. Among these, single-gloss paper, bleached or unbleached kraft paper is preferable, and bleached kraft paper, single-gloss paper, and single-gloss bleached kraft paper are preferable from the viewpoint of improving disintegration, and not from the viewpoint of improving opacity. Bleached kraft paper and unbleached kraft paper are preferable.
［樹脂層］
本実施形態における樹脂層は、紙基材の少なくとも一方の面に形成されている。かかる樹脂層は、水懸濁性高分子、アスペクト比が５０以上の板状無機化合物、およびカチオン性樹脂を含有する。これにより、樹脂層の顕微鏡拡大写真を撮ったときに、従来とは明らかに異なり、空隙のない稠密な膜を形成することができる。この樹脂層の空隙のない稠密な膜構造が、優れた水蒸気バリア性を発揮している。また、樹脂層を紙基材上に形成し、保護層を樹脂層上に直接形成する場合、均一な保護層の形成にも寄与して、より一層優れたガスバリア性、水蒸気バリア性を発現することができる。[Resin layer]
The resin layer in this embodiment is formed on at least one surface of the paper base material. Such a resin layer contains a water-suspendable polymer, a plate-like inorganic compound having an aspect ratio of 50 or more, and a cationic resin. As a result, when a microscopic magnified photograph of the resin layer is taken, it is possible to form a dense film without voids, which is clearly different from the conventional one. The dense film structure of the resin layer without voids exhibits excellent water vapor barrier properties. Further, when the resin layer is formed on the paper base material and the protective layer is directly formed on the resin layer, it also contributes to the formation of a uniform protective layer and exhibits further excellent gas barrier property and water vapor barrier property. be able to.
（水懸濁性高分子）
水懸濁性高分子は、水に懸濁することが可能な高分子であり、樹脂層を形成する際に、水を分散媒とした塗料を調製することを容易にする。水懸濁性高分子は、樹脂層の形成においてバインダーとして機能するため、板状無機化合物等を含有する樹脂層を均一に形成することができる。
水懸濁性高分子は、樹脂層に柔軟性を持たせ、加工時の耐久性を高める観点から熱可塑性樹脂が好ましく、オレフィン・不飽和カルボン酸系共重合体、スチレン・ブタジエン系共重合体、およびスチレン・アクリル系共重合体よりなる群から選ばれる１種以上を含むことが好ましく、前記群から選ばれる１種以上であることがより好ましい。(Water-suspendable polymer)
The water-suspendable polymer is a polymer that can be suspended in water, and facilitates the preparation of a coating material using water as a dispersion medium when forming a resin layer. Since the water-suspendable polymer functions as a binder in the formation of the resin layer, the resin layer containing a plate-like inorganic compound or the like can be uniformly formed.
The water-suspendable polymer is preferably a thermoplastic resin from the viewpoint of giving flexibility to the resin layer and enhancing durability during processing, and is an olefin / unsaturated carboxylic acid-based copolymer and a styrene / butadiene-based copolymer. , And one or more selected from the group consisting of styrene / acrylic copolymers, and more preferably one or more selected from the above group.
（オレフィン・不飽和カルボン酸系共重合体）
オレフィン・不飽和カルボン酸系共重合体は、オレフィン系単量体と不飽和カルボン酸系単量体との共重合体であり、たとえば、オレフィン系単量体と不飽和カルボン酸系単量体とを乳化重合することにより得られる共重合体である。
オレフィン・不飽和カルボン酸系共重合体のオレフィン系単量体としては、エチレン；プロピレン、ブチレン等のα−オレフィンが挙げられ、これらの中でも、好ましくはエチレンである。
オレフィン・不飽和カルボン酸系共重合体の不飽和カルボン酸系単量体は、不飽和カルボン酸単量体、および加水分解によりカルボン酸を形成する不飽和カルボン酸のエステル単量体を含む。オレフィン・不飽和カルボン酸系共重合体の不飽和カルボン酸系単量体としては、たとえば、アクリル酸、メタクリル酸、クロトン酸、ケイ皮酸、イタコン酸、フマル酸、マレイン酸、ブテントリカルボン酸等の不飽和カルボン酸およびそのエステル；イタコン酸モノエチルエステル、フマル酸モノブチルエステル、マレイン酸モノブチルエステル等の、少なくとも１個のカルボキシ基を有する不飽和ポリカルボン酸モノアルキルエステルが挙げられる。
オレフィン・不飽和カルボン酸系共重合体を構成する不飽和カルボン酸系単量体は、単独で、または２種以上用いてもよい。オレフィン・不飽和カルボン酸系共重合体は、オレフィンおよび不飽和カルボン酸系単量体と共重合可能なその他の単量体が少量共重合されていてもよい。
これらの中でも、オレフィン・不飽和カルボン酸系共重合体は、エチレン・アクリル酸系共重合体、およびエチレン・メタクリル酸系共重合体よりなる群から選ばれる１種以上であることが好ましく、エチレン・アクリル酸共重合体、エチレン・メタクリル酸共重合体、エチレン・アクリル酸メチル共重合体、エチレン・メタクリル酸メチル共重合体、エチレン・アクリル酸エチル共重合体、エチレン・メタクリル酸エチル共重合体、エチレン・アクリル酸ブチル共重合体、およびエチレン・メタクリル酸ブチル共重合体よりなる群から選ばれる１種以上であることがより好ましく、エチレン・アクリル酸共重合体であることがさらに好ましい。(Olefin / unsaturated carboxylic acid copolymer)
The olefin / unsaturated carboxylic acid-based copolymer is a copolymer of an olefin-based monomer and an unsaturated carboxylic acid-based monomer. For example, an olefin-based monomer and an unsaturated carboxylic acid-based monomer. It is a copolymer obtained by emulsifying and polymerizing.
Examples of the olefin-based monomer of the olefin / unsaturated carboxylic acid-based copolymer include ethylene; α-olefins such as propylene and butylene, and among these, ethylene is preferable.
The unsaturated carboxylic acid-based monomer of the olefin / unsaturated carboxylic acid-based copolymer includes an unsaturated carboxylic acid monomer and an ester monomer of an unsaturated carboxylic acid that forms a carboxylic acid by hydrolysis. Examples of the unsaturated carboxylic acid-based monomer of the olefin / unsaturated carboxylic acid-based copolymer include acrylic acid, methacrylic acid, crotonic acid, silicic acid, itaconic acid, fumaric acid, maleic acid, butentricarboxylic acid and the like. Unsaturated carboxylic acid and its ester; examples thereof include unsaturated polycarboxylic acid monoalkyl esters having at least one carboxy group, such as itaconic acid monoethyl ester, fumaric acid monobutyl ester, and maleic acid monobutyl ester.
The unsaturated carboxylic acid-based monomer constituting the olefin / unsaturated carboxylic acid-based copolymer may be used alone or in combination of two or more. The olefin / unsaturated carboxylic acid-based copolymer may be copolymerized with a small amount of an olefin and other monomers copolymerizable with the unsaturated carboxylic acid-based monomer.
Among these, the olefin / unsaturated carboxylic acid-based copolymer is preferably one or more selected from the group consisting of ethylene / acrylic acid-based copolymers and ethylene / methacrylic acid-based copolymers, and ethylene. -Acrylic acid copolymer, ethylene / methacrylic acid copolymer, ethylene / methyl acrylate copolymer, ethylene / methyl methacrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / ethyl methacrylate copolymer , Ethylene / butyl acrylate copolymer, and one or more selected from the group consisting of ethylene / butyl methacrylate copolymer, and more preferably ethylene / acrylate copolymer.
オレフィン・不飽和カルボン酸系共重合体は、不飽和カルボン酸系単量体単位の含有量が、好ましくは１ｍｏｌ％以上、より好ましくは１０ｍｏｌ％以上であり、そして、好ましくは５０ｍｏｌ％以下、より好ましくは３０ｍｏｌ％以下である。不飽和カルボン酸系単量体の含有量が上記範囲内であると、板状無機化合物の分散性に優れる。 The content of the unsaturated carboxylic acid-based monomer unit of the olefin / unsaturated carboxylic acid-based copolymer is preferably 1 mol% or more, more preferably 10 mol% or more, and preferably 50 mol% or less. It is preferably 30 mol% or less. When the content of the unsaturated carboxylic acid-based monomer is within the above range, the dispersibility of the plate-like inorganic compound is excellent.
オレフィン・不飽和カルボン酸系共重合体の重量平均分子量は、紙基材に付与する際の粘度および強度の観点から、好ましくは１万以上、より好ましくは１０万以上であり、そして、好ましくは１０００万以下、より好ましくは５００万以下である。オレフィン・不飽和カルボン酸系共重合体の重量平均分子量は、ゲルろ過クロマトグラフィー測定による標準ポリスチレン換算値により求めることができる。 The weight average molecular weight of the olefin / unsaturated carboxylic acid-based copolymer is preferably 10,000 or more, more preferably 100,000 or more, and preferably 100,000 or more, from the viewpoint of viscosity and strength when applied to a paper substrate. It is 10 million or less, more preferably 5 million or less. The weight average molecular weight of the olefin / unsaturated carboxylic acid-based copolymer can be determined by a standard polystyrene-equivalent value measured by gel filtration chromatography.
オレフィン・不飽和カルボン酸系共重合体として市販品を用いてもよく、たとえば、住友精化株式会社製の「ザイクセン（商品名）」等が挙げられる。 A commercially available product may be used as the olefin / unsaturated carboxylic acid-based copolymer, and examples thereof include "Zyxene (trade name)" manufactured by Sumitomo Seika Chemical Co., Ltd.
（スチレン・ブタジエン系共重合体）
スチレン・ブタジエン系共重合体としては、スチレン・ブタジエン系ゴム（ＳＢＲ）、変性スチレン・ブタジエン系ゴム（変性ＳＢＲ）等が挙げられる。
変性スチレン・ブタジエン系ゴムとしては、酸変性スチレン・ブタジエン系ゴム（酸変性ＳＢＲ）等が挙げられる。
スチレン・ブタジエン系共重合体として市販品を用いてもよく、たとえば、日本ゼオン株式会社製の「Ｎｉｐｏｌ ＬＸ４０７Ｓシリーズ（商品名）」、「Ｎｉｐｏｌ ＬＸ４０７ＢＰシリーズ（商品名）」等が挙げられる。(Styrene-butadiene copolymer)
Examples of the styrene-butadiene copolymer include styrene-butadiene rubber (SBR) and modified styrene-butadiene rubber (modified SBR).
Examples of the modified styrene-butadiene rubber include acid-modified styrene-butadiene rubber (acid-modified SBR).
Commercially available products may be used as the styrene-butadiene copolymer, and examples thereof include "Nipol LX407S series (trade name)" and "Nipol LX407BP series (trade name)" manufactured by Zeon Corporation.
（スチレン・アクリル系共重合体）
スチレン・アクリル系共重合体は、スチレン系化合物とアクリル系化合物との共重合体であり、たとえば、スチレン系化合物およびアクリル系化合物を含み、さらに必要に応じてこれらと共重合可能なその他の化合物を含む単量体を乳化重合することにより得られる共重合体である。
スチレン系化合物としては、たとえば、スチレン、α−メチルスチレン、ビニルトルエン、ｐ−ｔ−ブチルスチレン、クロロスチレン等が挙げられる。
アクリル系化合物としては、たとえば、アクリル酸、メタクリル酸等の不飽和カルボン酸系単量体；アクリル酸エステル、メタクリル酸エステル等の不飽和カルボン酸エステル系単量体等が挙げられる。
その他の化合物としては、たとえば、クロトン酸、ケイ皮酸、イタコン酸、フマル酸、マレイン酸、ブテントリカルボン酸等の不飽和カルボン酸系単量体；イタコン酸モノエチルエステル、フマル酸モノブチルエステルおよびマレイン酸モノブチルエステル等の少なくとも１個のカルボキシル基を有する不飽和ポリカルボン酸アルキルエステル系単量体；アクリルアミドプロパンスルホン酸、アクリル酸スルホエチルナトリウム塩、メタクリル酸スルホプロピルナトリウム塩等の不飽和スルホン酸系単量体またはその塩等が挙げられる。
スチレン系化合物としてはスチレン等が好適であり、またアクリル系化合物としてはアクリル酸、メタクリル酸が好適であり、その他の化合物としては、イタコン酸、フマル酸等が好適である。
スチレン・アクリル系共重合体として市販品を用いてもよく、たとえば、株式会社第一塗料製造所製の「ハービルシリーズＣ−３（商品名）」、ＢＡＳＦ社製の「ＡＣＲＯＮＡＬ４１６０」等が挙げられる。(Styrene / acrylic copolymer)
The styrene / acrylic copolymer is a copolymer of a styrene compound and an acrylic compound, and includes, for example, a styrene compound and an acrylic compound, and other compounds capable of copolymerizing with these, if necessary. It is a copolymer obtained by emulsifying and polymerizing a monomer containing.
Examples of the styrene compound include styrene, α-methylstyrene, vinyltoluene, pt-butylstyrene, chlorostyrene and the like.
Examples of the acrylic compound include unsaturated carboxylic acid-based monomers such as acrylic acid and methacrylic acid; unsaturated carboxylic acid ester-based monomers such as acrylic acid ester and methacrylic acid ester.
Other compounds include unsaturated carboxylic acid-based monomers such as crotonic acid, silicic acid, itaconic acid, fumaric acid, maleic acid, butentricarboxylic acid; itaconic acid monoethyl ester, fumaric acid monobutyl ester and Unsaturated polycarboxylic acid alkyl ester-based monomer having at least one carboxyl group such as maleic acid monobutyl ester; unsaturated sulfone such as acrylamide propane sulfonic acid, sulfoethyl acrylate sodium salt, sulfopropyl sodium methacrylate salt and the like Examples thereof include acid-based monomers and salts thereof.
As the styrene-based compound, styrene and the like are preferable, as the acrylic-based compound, acrylic acid and methacrylic acid are preferable, and as other compounds, itaconic acid, fumaric acid and the like are preferable.
Commercially available products may be used as the styrene / acrylic copolymer, and examples thereof include "Harville Series C-3 (trade name)" manufactured by Daiichi Paint Mfg. Co., Ltd. and "ACRONAL 4160" manufactured by BASF. Be done.
水懸濁性高分子の含有割合は、とくに限定されないが、樹脂層の全固形量中１５質量％以上が好ましく、２０質量％以上がより好ましく、２５質量％以上がさらに好ましく、５０質量％以上がさらに好ましく、６０質量％以上がさらに好ましく、そして９５質量％以下が好ましく、９０質量％以下がより好ましい。 The content ratio of the water-suspendable polymer is not particularly limited, but is preferably 15% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, and 50% by mass or more in the total solid content of the resin layer. Is more preferable, 60% by mass or more is further preferable, 95% by mass or less is preferable, and 90% by mass or less is more preferable.
（板状無機化合物）
板状無機化合物は、アスペクト比が５０以上であり、好ましくは８０以上であり、より好ましくは２００以上、さらに好ましくは３００以上、さらに好ましくは５００以上である。アスペクト比が大きいほど、水蒸気およびガスの移動距離が長くなる迷路効果により、水蒸気バリア性およびガスバリア性を向上させることができる。また、アスペクト比が大きいほど、少ない含有量で高い水蒸気バリア性を発揮することができる。アスペクト比の上限は、とくに限定されないが、入手容易性、紙基材上に樹脂層を形成する際の粘度等の観点から、好ましくは１００００以下、より好ましくは５０００以下、さらに好ましくは２０００以下である。
板状無機化合物のアスペクト比は、樹脂層を付与した方向に対して平行な厚さ方向（樹脂層の垂直方向）の断面について、電子顕微鏡を用いて拡大写真を撮影し、少なくとも３０個の板状無機化合物の長さおよび厚さを測定し、算術平均することにより平均長さおよび平均厚さを求める。そして、板状無機化合物の平均長さを平均厚さで除した値を板状無機化合物のアスペクト比とする。(Plate-shaped inorganic compound)
The plate-like inorganic compound has an aspect ratio of 50 or more, preferably 80 or more, more preferably 200 or more, still more preferably 300 or more, still more preferably 500 or more. The larger the aspect ratio, the longer the moving distance of water vapor and gas becomes. Due to the maze effect, the water vapor barrier property and the gas barrier property can be improved. Further, the larger the aspect ratio, the higher the water vapor barrier property can be exhibited with a smaller content. The upper limit of the aspect ratio is not particularly limited, but is preferably 10,000 or less, more preferably 5,000 or less, still more preferably 2,000 or less, from the viewpoint of availability, viscosity when forming a resin layer on a paper substrate, and the like. is there.
The aspect ratio of the plate-like inorganic compound is such that at least 30 plates are taken by taking an enlarged photograph using an electron microscope for a cross section in a thickness direction (vertical direction of the resin layer) parallel to the direction in which the resin layer is applied. The average length and thickness are obtained by measuring the length and thickness of the state-inorganic compound and performing arithmetic averaging. Then, the value obtained by dividing the average length of the plate-shaped inorganic compound by the average thickness is defined as the aspect ratio of the plate-shaped inorganic compound.
板状無機化合物は、上記のアスペクト比を有していれば、とくに限定されないが、合成マイカ、ベントナイト、およびカオリンよりなる群から選ばれる１種以上を含むことが好ましく、前記群から選ばれる１種以上であることがより好ましく、さらに好ましくは合成マイカ、およびカオリンよりなる群から選ばれる１種以上であり、さらに好ましくは合成マイカである。 The plate-like inorganic compound is not particularly limited as long as it has the above aspect ratio, but preferably contains one or more selected from the group consisting of synthetic mica, bentonite, and kaolin, and is selected from the above group1 More preferably, it is more than one species, more preferably one or more species selected from the group consisting of synthetic mica and kaolin, and even more preferably synthetic mica.
板状無機化合物の厚さ（平均厚さ）は、好ましくは２００ｎｍ以下、より好ましくは１２０ｎｍ以下、さらに好ましくは８０ｎｍ以下、さらに好ましくは５０ｎｍ以下である。厚さの下限は、とくに限定されないが、入手容易性、紙基材上に樹脂層を形成する際の粘度等の観点から、好ましくは１ｎｍ以上である。板状無機化合物の平均厚さが小さい方が、樹脂層中における板状無機化合物の積層数が多くなるため、少ない含有量で高い水蒸気バリア性を発揮することができる。 The thickness (average thickness) of the plate-like inorganic compound is preferably 200 nm or less, more preferably 120 nm or less, still more preferably 80 nm or less, still more preferably 50 nm or less. The lower limit of the thickness is not particularly limited, but is preferably 1 nm or more from the viewpoint of availability, viscosity when forming the resin layer on the paper substrate, and the like. When the average thickness of the plate-shaped inorganic compound is small, the number of laminated plate-shaped inorganic compounds in the resin layer is large, so that a high water vapor barrier property can be exhibited with a small content.
板状無機化合物の長さ（平均長さ）は、１μｍ以上１００μｍ以下であることが好ましい。長さが１μｍ以上であると、板状無機化合物が紙基材に対して平行に配列し易い。また、長さが１００μｍ以下であると板状無機化合物の一部が樹脂層から突出する懸念が少ない。なお、板状無機化合物の長さは、粒子径という表現で記載されることもある。 The length (average length) of the plate-shaped inorganic compound is preferably 1 μm or more and 100 μm or less. When the length is 1 μm or more, the plate-like inorganic compound tends to be arranged parallel to the paper substrate. Further, when the length is 100 μm or less, there is little concern that a part of the plate-like inorganic compound protrudes from the resin layer. The length of the plate-shaped inorganic compound may be described by the expression of particle size.
樹脂層中に含有される板状無機化合物の含有量は、とくに限定されず、水懸濁性高分子１００質量部に対して、好ましくは０．１質量部以上、より好ましくは１質量部以上、さらに好ましくは５質量部以上、さらに好ましくは１０質量部以上であり、そして好ましくは８００質量部以下、より好ましくは５００質量部以下、さらに好ましくは３００質量部以下、さらに好ましくは１００質量部以下、さらに好ましくは８０質量部以下、さらに好ましくは５０質量部以下、さらに好ましくは３０質量部以下、さらに好ましくは２０質量部以下である。板状無機化合物の含有量が、水懸濁性高分子１００質量部に対して０．１質量部以上であると、水蒸気バリア性が発現し易い。一方、８００質量部以下であると、板状無機化合物の一部が層表面から露出するのをより抑制でき、水蒸気バリア性をより向上させることができる。また、保護層を樹脂層上に直接形成する場合、保護層の塗工性が向上して均一な保護層が形成しやすくなり、ガスバリア性が向上しやすい。 The content of the plate-like inorganic compound contained in the resin layer is not particularly limited, and is preferably 0.1 part by mass or more, more preferably 1 part by mass or more, based on 100 parts by mass of the water-suspendable polymer. , More preferably 5 parts by mass or more, still more preferably 10 parts by mass or more, and preferably 800 parts by mass or less, more preferably 500 parts by mass or less, still more preferably 300 parts by mass or less, still more preferably 100 parts by mass or less. It is more preferably 80 parts by mass or less, further preferably 50 parts by mass or less, still more preferably 30 parts by mass or less, still more preferably 20 parts by mass or less. When the content of the plate-shaped inorganic compound is 0.1 part by mass or more with respect to 100 parts by mass of the water-suspending polymer, the water vapor barrier property is likely to be exhibited. On the other hand, when it is 800 parts by mass or less, it is possible to further suppress the exposure of a part of the plate-like inorganic compound from the layer surface, and it is possible to further improve the water vapor barrier property. Further, when the protective layer is directly formed on the resin layer, the coatability of the protective layer is improved, the uniform protective layer is easily formed, and the gas barrier property is easily improved.
樹脂層中に含有される板状無機化合物の割合は、とくに限定されず、水蒸気バリア性およびガスバリア性を向上する観点から、樹脂層の全固形量中０．１質量％以上が好ましく、１質量％以上がより好ましく、２質量％以上がさらに好ましく、５質量％以上がさらに好ましく、１０質量％以上がさらに好ましい。一方、保護層表面の平滑性を向上する観点から、８０質量％以下であることが好ましく、７０質量％以下であることがより好ましく、５０質量％以下であることがさらに好ましく、４０質量％以下であることがさらに好ましく、３０質量％以下であることがさらに好ましく、２０質量％以下であることがさらに好ましい。より少ない含有量で効果的であるといった観点から、板状無機化合物の中でもアスペクト比が大きく、厚さの小さい合成マイカが好適に使用できる。 The ratio of the plate-like inorganic compound contained in the resin layer is not particularly limited, and from the viewpoint of improving the water vapor barrier property and the gas barrier property, it is preferably 0.1% by mass or more based on the total solid amount of the resin layer, and 1 mass by mass. % Or more is more preferable, 2% by mass or more is further preferable, 5% by mass or more is further preferable, and 10% by mass or more is further preferable. On the other hand, from the viewpoint of improving the smoothness of the surface of the protective layer, it is preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 50% by mass or less, and 40% by mass or less. It is more preferably 30% by mass or less, and further preferably 20% by mass or less. From the viewpoint of being effective with a smaller content, synthetic mica having a large aspect ratio and a small thickness can be preferably used among the plate-like inorganic compounds.
（カチオン性樹脂）
樹脂層は、カチオン性樹脂を含有する。これにより、板状無機化合物の分散性が向上し、水蒸気バリア性が大きく向上する。板状無機化合物は、板状の平面部分がアニオン性に帯電しやすく、エッジ部分がカチオン性に帯電しやすいため、板状無機化合物が相互に立体的に連結した、いわゆるカードハウス構造をとることが知られている。このカードハウス構造のために、板状無機化合物の水分散液の粘度は非常に高くなる。一方、カードハウス構造は撹拌等により力を加えると簡単に壊れるため、板状無機化合物の水分散液はチキソトロピー性を示す。板状無機化合物の水分散液に、適切なカチオン性樹脂を添加すると、板状無機化合物のアニオン性に帯電した平面部分にカチオン性樹脂が吸着することによって、カードハウス構造が破壊されると考えられる。その結果、板状無機化合物が立体的に連結することが抑制され、板状無機化合物が紙基材平面に対して平行に積層しやすくなり、水蒸気バリア性の向上につながると推定される。さらに、ガスバリア性も向上すると推定される。(Cationic resin)
The resin layer contains a cationic resin. As a result, the dispersibility of the plate-like inorganic compound is improved, and the water vapor barrier property is greatly improved. The plate-shaped inorganic compound has a so-called card house structure in which the plate-shaped inorganic compounds are three-dimensionally connected to each other because the plate-shaped flat portion is easily charged anionic and the edge portion is easily charged cationically. It has been known. Due to this card house structure, the viscosity of the aqueous dispersion of the plate-like inorganic compound becomes very high. On the other hand, since the card house structure is easily broken when a force is applied by stirring or the like, the aqueous dispersion of the plate-like inorganic compound exhibits thixotropy. It is considered that when an appropriate cationic resin is added to the aqueous dispersion of the plate-shaped inorganic compound, the cationic resin is adsorbed on the anionically charged flat portion of the plate-shaped inorganic compound, and the card house structure is destroyed. Be done. As a result, it is presumed that the three-dimensional connection of the plate-shaped inorganic compounds is suppressed, the plate-shaped inorganic compounds are easily laminated in parallel with the plane of the paper substrate, and the water vapor barrier property is improved. Furthermore, it is estimated that the gas barrier property is also improved.
カチオン性樹脂としては、たとえば、ポリアミン樹脂、変性ポリアミド系樹脂（たとえば、アミン変性ポリアミド樹脂等のカチオン変性ポリアミド樹脂）、ポリアミドエピクロロヒドリン樹脂、ポリエチレンイミン樹脂、ポリアルキレンポリアミン樹脂、ポリアミド化合物、ポリアミドアミン・エピハロヒドリンまたはホルムアルデヒド縮合反応生成物、ポリアミン・エピハロヒドリンまたはホルムアルデヒド縮合反応生成物、ポリアミドポリ尿素・エピハロヒドリンまたはホルムアルデヒド縮合反応生成物、ポリアミンポリ尿素・エピハロヒドリンまたはホルムアルデヒド縮合反応生成物、ポリアミドアミンポリ尿素・エピハロヒドリンまたはホルムアルデヒド縮合反応生成物、ポリアミドポリ尿素化合物、ポリアミンポリ尿素化合物、ポリアミドアミンポリ尿素化合物およびポリアミドアミン化合物、ポリビニルピリジン、アミノ変性アクリルアミド系化合物、ポリビニルアミン樹脂、ポリジアリルジメチルアンモニウムクロリド等を挙げることができる。
これらの中でも、カチオン性樹脂は、ポリアミン樹脂、変性ポリアミド系樹脂、およびポリエチレンイミン樹脂より選ばれる少なくとも１種であることが好ましく、より好ましくは変性ポリアミド系樹脂であり、さらに好ましくはカチオン変性ポリアミド系樹脂であり、さらに好ましくはアミン変性ポリアミド樹脂である。Examples of the cationic resin include polyamine resins, modified polyamide resins (for example, cationic modified polyamide resins such as amine-modified polyamide resins), polyamide epichlorohydrin resins, polyethyleneimine resins, polyalkylene polyamine resins, polyamide compounds, and polyamides. Amin / epihalohydrin or formaldehyde condensation reaction product, polyamine / epihalohydrin or formaldehyde condensation reaction product, polyamide polyurea / epihalohydrin or formaldehyde condensation reaction product, polyamine polyurea / epihalohydrin or formaldehyde condensation reaction product, polyamide amine polyurea / epihalohydrin Alternatively, the formaldehyde condensation reaction product, polyamide polyurea compound, polyamine polyurea compound, polyamideamine polyurea compound and polyamideamine compound, polyvinylpyridine, amino-modified acrylamide compound, polyvinylamine resin, polydialyldimethylammonium chloride and the like can be mentioned. it can.
Among these, the cationic resin is preferably at least one selected from polyamine resin, modified polyamide resin, and polyethyleneimine resin, more preferably modified polyamide resin, and further preferably cationic modified polyamide resin. It is a resin, more preferably an amine-modified polyamide resin.
樹脂層中に含有されるカチオン性樹脂の含有量は、水蒸気バリア性をより向上させる観点から、板状無機化合物１００質量部に対して、好ましくは０．５質量部以上、より好ましくは１質量部以上、さらに好ましくは１０質量部以上、さらに好ましくは２０質量部以上、さらに好ましくは４０質量部以上、さらに好ましくは６０質量部以上であり、そして好ましくは３００質量部以下、より好ましくは２５０質量部以下、さらに好ましくは１５０質量部以下、さらに好ましくは１００質量部以下である。 The content of the cationic resin contained in the resin layer is preferably 0.5 parts by mass or more, more preferably 1 part by mass with respect to 100 parts by mass of the plate-shaped inorganic compound from the viewpoint of further improving the water vapor barrier property. More than parts, more preferably 10 parts by mass or more, still more preferably 20 parts by mass or more, still more preferably 40 parts by mass or more, still more preferably 60 parts by mass or more, and preferably 300 parts by mass or less, more preferably 250 parts by mass. Parts or less, more preferably 150 parts by mass or less, still more preferably 100 parts by mass or less.
樹脂層中に含有されるカチオン性樹脂の含有量は、水蒸気バリア性をより向上させる観点から、水懸濁性高分子１００質量部に対して、好ましくは０．１質量部以上、より好ましくは１質量部以上、さらに好ましくは３質量部以上、さらに好ましくは５質量部以上、さらに好ましくは８質量部以上、さらに好ましくは１０質量部以上であり、そして好ましくは１００質量部以下、より好ましくは５０質量部以下、さらに好ましくは４０質量部以下、さらに好ましくは３０質量部以下、さらに好ましくは２０質量部以下、さらに好ましくは１５質量部以下である。 The content of the cationic resin contained in the resin layer is preferably 0.1 part by mass or more, more preferably 0.1 part by mass or more, based on 100 parts by mass of the water-suspendable polymer, from the viewpoint of further improving the water vapor barrier property. 1 part by mass or more, more preferably 3 parts by mass or more, further preferably 5 parts by mass or more, still more preferably 8 parts by mass or more, still more preferably 10 parts by mass or more, and preferably 100 parts by mass or less, more preferably 100 parts by mass or more. It is 50 parts by mass or less, more preferably 40 parts by mass or less, further preferably 30 parts by mass or less, still more preferably 20 parts by mass or less, still more preferably 15 parts by mass or less.
樹脂層中に含有されるカチオン性樹脂の割合は、とくに限定されず、樹脂層の全固形量中０．１質量％以上が好ましく、０．２質量％以上がより好ましく、０．５質量％以上がさらに好ましく、１質量％以上がさらに好ましく、５質量％以上がさらに好ましく、そして２０質量％以下であることが好ましく、１５質量％以下であることがより好ましい。 The proportion of the cationic resin contained in the resin layer is not particularly limited, and is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and 0.5% by mass, based on the total solid content of the resin layer. The above is more preferable, 1% by mass or more is further preferable, 5% by mass or more is further preferable, 20% by mass or less is preferable, and 15% by mass or less is more preferable.
樹脂層には、水懸濁性高分子、板状無機化合物、およびカチオン性樹脂以外に、必要に応じて適宜、顔料、上述したカチオン性樹脂以外の分散剤、界面活性剤、消泡剤、濡れ剤、染料、色合い調整剤、増粘剤、水溶性高分子等の助剤を添加することができる。 In addition to the water-suspendable polymer, the plate-like inorganic compound, and the cationic resin, the resin layer may contain pigments, dispersants other than the above-mentioned cationic resins, surfactants, defoaming agents, as appropriate. Auxiliary agents such as wetting agents, dyes, color modifiers, thickeners, and water-soluble polymers can be added.
樹脂層の厚さは、好ましくは１μｍ以上、より好ましくは３μｍ以上であり、そして好ましくは３０μｍ以下、より好ましくは２０μｍ以下である。
また、樹脂層の形成量（以下、塗工量ともいう。）は、固形分として、好ましくは１ｇ／ｍ２以上、より好ましくは３ｇ／ｍ２以上であり、そして好ましくは３０ｇ／ｍ２以下、より好ましくは２０ｇ／ｍ２以下である。The thickness of the resin layer is preferably 1 μm or more, more preferably 3 μm or more, and preferably 30 μm or less, more preferably 20 μm or less.
The amount of the resin layer formed (hereinafter, also referred to as the coating amount) is preferably 1 g / m 2 or more, more preferably 3 g / m 2 or more, and preferably 30 g / m 2 or less as a solid content. , More preferably 20 g / m 2 or less.
［保護層］
本実施形態における保護層は、紙基材の少なくとも一方の面に形成されている。かかる保護層は、水溶性高分子を含有する。保護層は、樹脂層上に形成されていてもよく、紙基材上に形成されていてもよい。樹脂層上に形成される場合、ガスバリア性、とくに酸素バリア性に優れるとともに、樹脂層を保護してバリア性を向上できる。また、水の存在下で離解性を高めて、リサイクル性により優れた紙積層体を得ることができる。一方、保護層を紙基材上に形成することによって、より均一な樹脂層を形成し、バリア性をより向上することができる。[Protective layer]
The protective layer in this embodiment is formed on at least one surface of the paper substrate. Such a protective layer contains a water-soluble polymer. The protective layer may be formed on a resin layer or a paper base material. When formed on the resin layer, it is excellent in gas barrier property, particularly oxygen barrier property, and can protect the resin layer to improve the barrier property. In addition, it is possible to improve the disintegration property in the presence of water and obtain a paper laminate having better recyclability. On the other hand, by forming the protective layer on the paper base material, a more uniform resin layer can be formed and the barrier property can be further improved.
（水溶性高分子）
水溶性高分子としては、たとえば、ポリビニルアルコール、変性ポリビニルアルコール、デンプンおよびその誘導体、セルロース誘導体、ポリビニルピロリドン、ウレタン系樹脂、ポリアクリル酸およびその塩、カゼイン、ポリエチレンイミン等が挙げられる。(Water-soluble polymer)
Examples of the water-soluble polymer include polyvinyl alcohol, modified polyvinyl alcohol, starch and its derivatives, cellulose derivatives, polyvinylpyrrolidone, urethane resins, polyacrylic acids and salts thereof, casein, polyethyleneimine and the like.
これらの中でも、ガスバリア性がより優れていることから、完全ケン化もしくは部分ケン化したポリビニルアルコール、変性ポリビニルアルコール、ポリエチレンイミンが好ましく、ポリビニルアルコールおよび変性ポリビニルアルコールよりなる群から選ばれる１種以上を含むことがより好ましく、前記群から選ばれる１種以上であることがさらに好ましい。変性ポリビニルアルコールとしては、たとえば、エチレン変性ポリビニルアルコール、カルボキシ変性ポリビニルアルコール、珪素変性ポリビニルアルコール、アセトアセチル変性ポリビニルアルコール、ジアセトン変性ポリビニルアルコール等が挙げられる。 Among these, completely saponified or partially saponified polyvinyl alcohol, modified polyvinyl alcohol, and polyethyleneimine are preferable because they have more excellent gas barrier properties, and one or more selected from the group consisting of polyvinyl alcohol and modified polyvinyl alcohol is selected. It is more preferable to include, and it is further preferable that it is one or more selected from the above group. Examples of the modified polyvinyl alcohol include ethylene-modified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, silicon-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, and diacetone-modified polyvinyl alcohol.
水溶性高分子の含有量は、保護層の全固形量中５０質量％以上が好ましく、６０質量％以上が好ましく、７０質量％以上がより好ましく、そして１００質量％以下が好ましい。 The content of the water-soluble polymer is preferably 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, and preferably 100% by mass or less based on the total solid content of the protective layer.
保護層には、樹脂層と同様に、前記した板状無機化合物を含有させてもよい。板状無機化合物としては、バリア性を向上させる観点から、合成マイカ、ベントナイトおよびカオリンよりなる群から選ばれる少なくとも１種であることが好ましい。保護層に含有させる板状無機化合物は、樹脂層に含有させる板状無機化合物と同一の種類であってもよいし、異なる種類であってもよい。
板状無機化合物を保護層に含有させる場合、板状無機化合物の含有量は、とくに限定されないが、保護層の水溶性高分子１００質量部に対して、１質量部以上が好ましく、５質量部以上がより好ましく、そして８０質量部以下が好ましく、７０質量部以下がより好ましい。板状無機化合物の中でも、保護層の水溶性高分子１００質量部に対して、アスペクト比が大きく、厚さの小さい合成マイカを５質量部以上１５質量部以下含有させることが好ましい。さらに、合成マイカと他の板状無機化合物（たとえば、カオリン等）を併用する場合、他の板状無機化合物の含有量は、保護層の水溶性高分子１００質量部に対して、好ましくは２０質量部以上であり、そして、好ましくは８０質量部以下である。Similar to the resin layer, the protective layer may contain the above-mentioned plate-like inorganic compound. The plate-like inorganic compound is preferably at least one selected from the group consisting of synthetic mica, bentonite and kaolin from the viewpoint of improving the barrier property. The plate-shaped inorganic compound contained in the protective layer may be of the same type as the plate-shaped inorganic compound contained in the resin layer, or may be of a different type.
When the plate-shaped inorganic compound is contained in the protective layer, the content of the plate-shaped inorganic compound is not particularly limited, but is preferably 1 part by mass or more and 5 parts by mass with respect to 100 parts by mass of the water-soluble polymer of the protective layer. The above is more preferable, 80 parts by mass or less is preferable, and 70 parts by mass or less is more preferable. Among the plate-like inorganic compounds, it is preferable to contain 5 parts by mass or more and 15 parts by mass or less of synthetic mica having a large aspect ratio and a small thickness with respect to 100 parts by mass of the water-soluble polymer of the protective layer. Further, when synthetic mica is used in combination with another plate-shaped inorganic compound (for example, kaolin), the content of the other plate-shaped inorganic compound is preferably 20 with respect to 100 parts by mass of the water-soluble polymer of the protective layer. It is at least 80 parts by mass, and preferably 80 parts by mass or less.
保護層は、水溶性高分子以外に、必要に応じて適宜、板状無機化合物、顔料、カチオン性樹脂、上述したカチオン性樹脂以外の分散剤、界面活性剤、消泡剤、濡れ剤、染料、色合い調整剤、増粘剤等の助剤を添加することが可能である。 In addition to the water-soluble polymer, the protective layer is appropriately composed of a plate-like inorganic compound, a pigment, a cationic resin, a dispersant other than the above-mentioned cationic resin, a surfactant, a defoaming agent, a wetting agent, and a dye. , Tone adjusters, thickeners and other auxiliaries can be added.
保護層の厚さは、好ましくは０．１μｍ以上、より好ましくは０．５μｍ以上であり、そして好ましくは１０μｍ以下、より好ましくは５μｍ以下である。
また、保護層の形成量（以下、塗工量ともいう。）は、固形分として、好ましくは０．１ｇ／ｍ２以上、より好ましくは０．５ｇ／ｍ２以上であり、そして好ましくは１０ｇ／ｍ２以下、より好ましくは５ｇ／ｍ２以下である。The thickness of the protective layer is preferably 0.1 μm or more, more preferably 0.5 μm or more, and preferably 10 μm or less, more preferably 5 μm or less.
The amount of the protective layer formed (hereinafter, also referred to as the coating amount) is preferably 0.1 g / m 2 or more, more preferably 0.5 g / m 2 or more, and preferably 10 g as the solid content. / M 2 or less, more preferably 5 g / m 2 or less.
［シーラント層］
本実施形態では、紙積層体の少なくとも一方の最外層にシーラント層をさらに有することが好ましい。すなわち、シーラント層は、樹脂層および保護層を形成した側の紙基材から最も遠い層の上、または樹脂層および保護層を形成していない側の紙基材から最も遠い層の上（樹脂層および保護層を形成していない側に他の層がない場合は紙基材の上）、のどちらか一方または両方に形成することができる。[Sealant layer]
In the present embodiment, it is preferable to further have a sealant layer on at least one outermost layer of the paper laminate. That is, the sealant layer is on the layer farthest from the paper base material on the side where the resin layer and the protective layer are formed, or on the layer farthest from the paper base material on the side where the resin layer and the protective layer are not formed (resin). It can be formed on one or both of (on the paper substrate if there is no other layer on the side that does not form the layer and the protective layer).
シーラント層は、加熱や超音波で溶融し接着する層であり、紙積層体同士をヒートシール等により相互に結合させることができる層である。 The sealant layer is a layer that melts and adheres by heating or ultrasonic waves, and is a layer that can bond the paper laminates to each other by heat sealing or the like.
シーラント層は、たとえば、ポリオレフィン（ポリエチレン、ポリプロピレン等）、変性ポリオレフィン、エチレン・酢酸ビニル系重合体、ポリ酢酸ビニル重合体等の合成樹脂を溶融押出ラミ法やドライラミ法によって積層することによって形成することができる。また、シーラント層は、たとえば、ポリオレフィン、変性ポリオレフィン、エチレン・酢酸ビニル系重合体、ポリ酢酸ビニル重合体等の合成樹脂の乳化分散液を塗工することによって形成することもできる。 The sealant layer is formed by laminating synthetic resins such as polyolefin (polyethylene, polypropylene, etc.), modified polyolefin, ethylene-vinyl acetate polymer, polyvinyl acetate polymer, etc. by melt extrusion laminating method or dry laminating method. Can be done. The sealant layer can also be formed by applying, for example, an emulsified dispersion of a synthetic resin such as a polyolefin, a modified polyolefin, an ethylene-vinyl acetate polymer, or a polyvinyl acetate polymer.
シーラント層は、生分解性樹脂を含有することが好ましい。生分解性樹脂の具体例としては、とくに限定されず、たとえば、ポリ乳酸（ＰＬＡ）．ポリブチレンサクシネート（ＰＢＳ）ポリブチレンサクシネートアジペート（ＰＢＳＡ）、３−ヒドロキシブタン酸・３−ヒドロキシヘキサン酸共重合体（ＰＨＢＨ）等が挙げられる。 The sealant layer preferably contains a biodegradable resin. Specific examples of the biodegradable resin are not particularly limited, and for example, polylactic acid (PLA). Polybutylene succinate (PBS) Polybutylene succinate adipate (PBSA), 3-hydroxybutanoic acid / 3-hydroxyhexanoic acid copolymer (PHBH) and the like can be mentioned.
シーラント層の厚さは、好ましくは１μｍ以上、より好ましくは３μｍ以上であり、そして好ましくは５０μｍ以下、より好ましくは３０μｍ以下である。
また、シーラント層の形成量は、固形分として、好ましくは１ｇ／ｍ２以上、より好ましくは３ｇ／ｍ２以上であり、そして好ましくは５０ｇ／ｍ２以下より好ましくは３０ｇ／ｍ２以下である。The thickness of the sealant layer is preferably 1 μm or more, more preferably 3 μm or more, and preferably 50 μm or less, more preferably 30 μm or less.
The amount of the sealant layer formed is preferably 1 g / m 2 or more, more preferably 3 g / m 2 or more, and preferably 50 g / m 2 or less and more preferably 30 g / m 2 or less as a solid content. ..
＜紙積層体の製造方法＞
本実施形態の紙積層体は、紙基材上の少なくとも一方の面に、樹脂層と保護層とが形成され、必要によりシーラント層が形成される。
各層の形成方法は、とくに限定されないが、少なくとも樹脂層と保護層は、塗工法により形成することが好ましい。本実施形態の好ましい一態様として、具体的には、紙基材上に樹脂層塗料を塗工し、乾燥して、樹脂層を形成し、さらに樹脂層上に保護層塗料を塗工し、乾燥して、保護層を形成すればよい。各層は、塗料を逐次塗工および乾燥させて形成してもよく、同時多層塗工した後に乾燥させて形成してもよい。同時多層塗工としては、紙基材における表面と裏面の塗工層を両面同時に、または片面の下層および上層を同時に塗工してもよい。<Manufacturing method of paper laminate>
In the paper laminate of the present embodiment, a resin layer and a protective layer are formed on at least one surface of the paper base material, and a sealant layer is formed if necessary.
The method for forming each layer is not particularly limited, but it is preferable that at least the resin layer and the protective layer are formed by a coating method. As a preferred embodiment of the present embodiment, specifically, a resin layer paint is applied on a paper base material, dried to form a resin layer, and a protective layer paint is further applied on the resin layer. It may be dried to form a protective layer. Each layer may be formed by sequentially applying and drying the paint, or may be formed by simultaneously applying multiple layers and then drying. As the simultaneous multilayer coating, the coating layers on the front surface and the back surface of the paper substrate may be coated simultaneously on both sides, or the lower layer and the upper layer on one side may be coated simultaneously.
塗料を塗工するための塗工設備にはとくに制限はなく、公知の設備を用いればよい。塗工設備としては、たとえば、メイヤーバー、ブレードコーター、バーコーター、エアナイフコーター、スリットダイコーター、カーテンコーター、グラビアコーター、マイクログラビアコーター、ゲートロールコーター、サイズプレスコーター等が挙げられる。とくに、樹脂層の形成には、メイヤーバー、ブレードコーター、バーコーター、エアナイフコーター、スリットダイコーター等の塗工表面をスクレイプするコーターが、板状無機化合物の配向を促す点で好ましい。 The coating equipment for applying the paint is not particularly limited, and known equipment may be used. Examples of the coating equipment include a Mayer bar, a blade coater, a bar coater, an air knife coater, a slit die coater, a curtain coater, a gravure coater, a micro gravure coater, a gate roll coater, and a size press coater. In particular, for forming the resin layer, a coater that scrapes the coated surface such as a Mayer bar, a blade coater, a bar coater, an air knife coater, and a slit die coater is preferable because it promotes the orientation of the plate-like inorganic compound.
塗工層を乾燥するための乾燥設備には、とくに限定されず、公知の設備を用いることができる。乾燥設備としては、たとえば、熱風乾燥機、赤外線乾燥機、ガスバーナー、熱板等が挙げられる。また、乾燥温度は、乾燥時間等を考慮して、適宜設定すればよい。 The drying equipment for drying the coating layer is not particularly limited, and known equipment can be used. Examples of the drying equipment include a hot air dryer, an infrared dryer, a gas burner, a hot plate, and the like. Further, the drying temperature may be appropriately set in consideration of the drying time and the like.
塗料の溶媒としては、とくに限定されず、たとえば、水またはエタノール、イソプロピルアルコール、メチルエチルケトンもしくはトルエン等の有機溶媒を用いることができる。
これらの中でも、本実施形態において、揮発性有機溶媒の問題を生じない観点から、塗料の分散媒としては、水が好ましい。すなわち、樹脂層および保護層の塗料は、水系組成物であることが好ましい。The solvent for the coating material is not particularly limited, and for example, water or an organic solvent such as ethanol, isopropyl alcohol, methyl ethyl ketone or toluene can be used.
Among these, in the present embodiment, water is preferable as the dispersion medium of the coating material from the viewpoint of not causing the problem of the volatile organic solvent. That is, the coating material for the resin layer and the protective layer is preferably an aqueous composition.
塗料の固形分濃度は、とくに限定されず、塗工性および乾燥容易性の観点から適宜選択すればよいが、好ましくは３質量％以上、より好ましくは５質量％以上、さらに好ましくは１０質量％以上であり、そして、好ましくは８０質量％以下、より好ましくは７０質量％以下、さらに好ましくは６０質量％以下である。 The solid content concentration of the coating material is not particularly limited and may be appropriately selected from the viewpoint of coatability and easiness of drying, but is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass. It is more than 80% by mass, more preferably 70% by mass or less, still more preferably 60% by mass or less.
本実施形態の紙積層体は、上記の優れた水蒸気バリア性およびガスバリア性を活かして、コーヒー、菓子、牛乳等の食品、医薬品、医療品、電子部品等の包装用材料として好適に用いることができる。これらの中でも、折割れに耐性を有することから、軟包装用材料、重袋用の紙容器、ミルクカートン等の包装容器に好適に用いることができる。 The paper laminate of the present embodiment can be suitably used as a packaging material for foods such as coffee, confectionery, milk, pharmaceuticals, medical products, electronic parts, etc. by taking advantage of the above-mentioned excellent water vapor barrier property and gas barrier property. it can. Among these, since it has resistance to cracking, it can be suitably used for flexible packaging materials, paper containers for heavy bags, packaging containers such as milk cartons, and the like.
以下に実施例と比較例とを挙げて本発明の特徴をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り適宜変更することができる。したがって、本発明の範囲は以下に示す具体例により限定的に解釈されるべきものではない。なお、実施例および比較例中の「部」および「％」は、とくに断らない限り、それぞれ「質量部」および「質量％」を示す。 Hereinafter, the features of the present invention will be described in more detail with reference to Examples and Comparative Examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed in a limited manner by the specific examples shown below. Unless otherwise specified, "parts" and "%" in Examples and Comparative Examples indicate "parts by mass" and "% by mass", respectively.
［実施例１］
・板状無機化合物の水分散液の調製
板状無機化合物（エンジニアードカオリン、粒子径１０μｍ、アスペクト比１００、厚さ１００ｎｍ、商品名：バリサーフＨＸ、イメリス社製）を水に分散し、固形分５５％の水分散液Ａを得た。[Example 1]
-Preparation of aqueous dispersion of plate-shaped inorganic compound Plate-shaped inorganic compound (engineered kaolin, particle size 10 μm, aspect ratio 100, thickness 100 nm, trade name: Varisurf HX, manufactured by Imeris) is dispersed in water and solid content. A 55% aqueous dispersion A was obtained.
・樹脂層塗料の調製
オレフィン・不飽和カルボン酸系共重合体として自己乳化型ポリオレフィン分散液（固形分２９．２％、商品名：ザイクセンＡＣ、住友精化株式会社製、エチレン・アクリル酸共重合体）３４．２部に対して、上記の板状無機化合物の水分散液Ａを３６．４部加えて撹拌した。これに、カチオン性樹脂として変性ポリアミド系樹脂（固形分５３％、商品名：ＳＰＩ２０３（５０）Ｈ、田岡化学工業株式会社製）を０．７５部加えて撹拌した。さらに、２５％アンモニア水溶液を０．３０部加えて撹拌した。さらに、希釈水を加えて固形分濃度４０％とし、樹脂層塗料を得た。-Preparation of resin layer paint Self-emulsifying polyolefin dispersion as an olefin / unsaturated carboxylic acid copolymer (solid content 29.2%, trade name: Zyxen AC, manufactured by Sumitomo Seika Co., Ltd., ethylene / acrylic acid copolymer weight 36.4 parts of the above-mentioned aqueous dispersion A of the plate-like inorganic compound was added to 34.2 parts of the mixture), and the mixture was stirred. To this, 0.75 parts of a modified polyamide resin (solid content 53%, trade name: SPI203 (50) H, manufactured by Taoka Chemical Industry Co., Ltd.) as a cationic resin was added and stirred. Further, 0.30 part of a 25% aqueous ammonia solution was added and stirred. Further, diluted water was added to bring the solid content concentration to 40%, and a resin layer coating material was obtained.
・保護層塗料の調製
水溶性高分子としてエチレン変性ポリビニルアルコール（完全ケン化型、商品名：エクセバールＡＱ−４１０、株式会社クラレ製）の固形分１５％の水溶液６６．７部に、ポリエチレンイミン（固形分３０％、商品名：エポミンＰ−１０００、株式会社日本触媒製）０．１７部を加え、さらに希釈水を加え、固形分濃度１０％とし、保護層塗料を得た。-Preparation of protective layer paint Polyethyleneimine (completely saponified type, trade name: Excelval AQ-410, manufactured by Kuraray Co., Ltd.) in 66.7 parts of an aqueous solution having a solid content of 15% as a water-soluble polymer. A solid content of 30%, trade name: Epomin P-1000, manufactured by Nippon Catalyst Co., Ltd.) was added in an amount of 0.17 parts, and diluted water was further added to bring the solid content concentration to 10% to obtain a protective layer coating material.
・紙積層体の作製
得られた樹脂層塗料を用いて、乾燥後の塗工量が１２．０ｇ／ｍ２となるように、片艶晒クラフト紙（王子マテリア株式会社製）の平滑面の逆側の面（以下、非艶面や非平滑面ともいう。）にメイヤーバーで塗工した後、熱風乾燥機内で１２０℃、１分間乾燥して樹脂層（厚さ：１２μｍ）を形成した。さらに、保護層塗料を用いて、乾燥後の塗工量が３．０ｇ／ｍ２となるように、樹脂層上にメイヤーバーで塗工した後、熱風乾燥機内で１２０℃、１分間乾燥して保護層（厚さ：３μｍ）を形成し、紙積層体を得た。紙基材として使用した片艶晒クラフト紙は、坪量６５ｇ／ｍ２、厚さ６２μｍ、密度０．７６ｇ／ｍ３、平滑面の王研式平滑度４２７秒、非平滑面の王研式平滑度１７秒であった。-Preparation of paper laminate Using the obtained resin layer paint, the smooth surface of single-gloss bleached kraft paper (manufactured by Oji Materia Co., Ltd.) so that the coating amount after drying is 12.0 g / m 2. The opposite surface (hereinafter, also referred to as non-glossy surface or non-smooth surface) was coated with a Mayer bar and then dried in a hot air dryer at 120 ° C. for 1 minute to form a resin layer (thickness: 12 μm). .. Further, using a protective layer paint, the resin layer is coated with a Mayer bar so that the coating amount after drying is 3.0 g / m 2, and then dried in a hot air dryer at 120 ° C. for 1 minute. A protective layer (thickness: 3 μm) was formed to obtain a paper laminate. The single-gloss bleached kraft paper used as the paper base material has a basis weight of 65 g / m 2 , a thickness of 62 μm, a density of 0.76 g / m 3 , a smooth surface of Oken type smoothness of 427 seconds, and a non-smooth surface of Oken type. The smoothness was 17 seconds.
［実施例２］
・樹脂層塗料の調製
板状無機化合物の水分散液Ｂ（合成マイカ、粒子径６μｍ、アスペクト比１２００、厚さ５ｎｍ、固形分６％、商品名：ＮＴＯ−０５、トピー工業株式会社製）３０．０部に、撹拌しながらオレフィン・不飽和カルボン酸系共重合体として自己乳化型ポリオレフィン分散液（固形分２９．２％、商品名：ザイクセンＡＣ、住友精化株式会社製、エチレン・アクリル酸共重合体）３４．２部を加えて撹拌した。これに、カチオン性樹脂として変性ポリアミド系樹脂（固形分５３％、商品名：ＳＰＩ２０３（５０）Ｈ、田岡化学工業株式会社製）を２．５５部加えて撹拌した。さらに、２５％アンモニア水溶液を０．３０部加えて撹拌した。さらに、希釈水を加えて固形分濃度１９％とし、樹脂層塗料を得た。[Example 2]
-Preparation of resin layer paint Water dispersion B of plate-shaped inorganic compound (synthetic mica, particle size 6 μm, aspect ratio 1200, thickness 5 nm, solid content 6%, trade name: NTO-05, manufactured by Topy Industry Co., Ltd.) 30 A self-emulsifying polyolefin dispersion (solid content 29.2%, trade name: Zyxen AC, manufactured by Sumitomo Seika Co., Ltd., ethylene / acrylic acid) as an olefin / unsaturated carboxylic acid-based copolymer in 0.0 part with stirring. Copolymer) 34.2 parts was added and stirred. To this, 2.55 parts of a modified polyamide resin (solid content 53%, trade name: SPI203 (50) H, manufactured by Taoka Chemical Industry Co., Ltd.) was added as a cationic resin and stirred. Further, 0.30 part of a 25% aqueous ammonia solution was added and stirred. Further, diluted water was added to bring the solid content concentration to 19%, and a resin layer coating material was obtained.
・保護層塗料の調製
水溶性高分子としてエチレン変性ポリビニルアルコール（完全ケン化型、商品名：エクセバールＡＱ−４１０４、株式会社クラレ製）の固形分１２％の水溶液８３．３部に、上記の板状無機化合物の水分散液Ｂを１６．７部加えて撹拌し、さらに上記の板状無機化合物の水分散液Ａを９．１部加え、さらに、希釈水を加えて固形分濃度１０％とし、保護層塗料を得た。-Preparation of protective layer paint 83.3 parts of an aqueous solution of ethylene-modified polyvinyl alcohol (completely saponified type, trade name: Excelval AQ-4104, manufactured by Kuraray Co., Ltd.) as a water-soluble polymer with a solid content of 12%, the above plate Add 16.7 parts of the aqueous dispersion B of the state-inorganic compound and stir, add 9.1 parts of the above-mentioned aqueous dispersion A of the plate-like inorganic compound, and add diluted water to make the solid content concentration 10%. , Obtained protective layer paint.
・紙積層体の作製
得られた樹脂層塗料を用いて、乾燥後の塗工量が６．０ｇ／ｍ２となるように、片艶晒クラフト紙（王子マテリア株式会社製）の平滑面の逆側の面（非平滑面）にメイヤーバーで塗工した後、熱風乾燥機内で１２０℃、１分間乾燥して樹脂層（厚さ：６μｍ）を形成した。さらに、保護層塗料を用いて、乾燥後の塗工量が３．０ｇ／ｍ２となるように、樹脂層上にメイヤーバーで塗工した後、熱風乾燥機内で１２０℃、１分間乾燥して保護層（厚さ：３μｍ）を形成し、紙積層体を得た。紙基材として使用した片艶晒クラフト紙は、坪量６５ｇ／ｍ２、厚さ６２μｍ、密度０．７６ｇ／ｍ３、平滑面の王研式平滑度４２７秒、非平滑面の王研式平滑度１７秒であった。-Preparation of paper laminate Using the obtained resin layer paint, the smooth surface of single-gloss bleached kraft paper (manufactured by Oji Materia Co., Ltd.) so that the coating amount after drying is 6.0 g / m 2. The opposite surface (non-smooth surface) was coated with a Mayer bar and then dried in a hot air dryer at 120 ° C. for 1 minute to form a resin layer (thickness: 6 μm). Further, using a protective layer paint, the resin layer is coated with a Mayer bar so that the coating amount after drying is 3.0 g / m 2, and then dried in a hot air dryer at 120 ° C. for 1 minute. A protective layer (thickness: 3 μm) was formed to obtain a paper laminate. The single-gloss bleached kraft paper used as the paper base material has a basis weight of 65 g / m 2 , a thickness of 62 μm, a density of 0.76 g / m 3 , a smooth surface of Oken type smoothness of 427 seconds, and a non-smooth surface of Oken type. The smoothness was 17 seconds.
［実施例３］
実施例１の紙積層体の作製において、片艶晒クラフト紙（王子マテリア株式会社製）の平滑面の逆側の面（非平滑面）に代えて、片艶晒クラフト紙（王子マテリア株式会社製）の平滑面（艶面）に樹脂層および保護層を形成した以外は、実施例１と同様にして紙積層体を得た。[Example 3]
In the production of the paper laminate of Example 1, instead of the surface opposite to the smooth surface (non-smooth surface) of the single-gloss bleached kraft paper (manufactured by Oji Materia Co., Ltd.), the single-gloss bleached kraft paper (Oji Materia Co., Ltd.) A paper laminate was obtained in the same manner as in Example 1 except that a resin layer and a protective layer were formed on the smooth surface (glossy surface) of (manufactured by).
［実施例４］
実施例１の紙積層体の作製において、片艶晒クラフト紙（王子マテリア株式会社製）の平滑面の逆側の面（非平滑面）に代えて、片艶晒クラフト紙（王子エフテックス株式会社製）の平滑面の逆側の面（非平滑面）に樹脂層および保護層を形成した以外は、実施例１と同様にして紙積層体を得た。紙基材として使用した片艶晒クラフト紙は、坪量５０ｇ／ｍ２、厚さ６２．３μｍ、密度０．８０ｇ／ｃｍ３、平滑面の王研式平滑度２８７秒、非平滑面の王研式平滑度１７秒であった。[Example 4]
In the production of the paper laminate of Example 1, instead of the surface opposite to the smooth surface (non-smooth surface) of the single-gloss bleached kraft paper (manufactured by Oji Materia Co., Ltd.), the single-gloss bleached kraft paper (Oji F-Tex Co., Ltd.) A paper laminate was obtained in the same manner as in Example 1 except that a resin layer and a protective layer were formed on the surface (non-smooth surface) opposite to the smooth surface (manufactured by the company). The single-gloss bleached kraft paper used as the paper base material has a basis weight of 50 g / m 2 , a thickness of 62.3 μm, a density of 0.80 g / cm 3 , a smooth surface Oken-style smoothness of 287 seconds, and a non-smooth surface king. The sharpness was 17 seconds.
［実施例５］
実施例２の紙積層体の作製において、片艶晒クラフト紙（王子マテリア株式会社製）の平滑面の逆側の面（非平滑面）に代えて、片艶晒クラフト紙（王子エフテックス株式会社製）の平滑面の逆側の面（非平滑面）に樹脂層および保護層を形成した以外は、実施例２と同様にして紙積層体を得た。[Example 5]
In the production of the paper laminate of Example 2, instead of the surface opposite to the smooth surface (non-smooth surface) of the single-gloss bleached kraft paper (manufactured by Oji Materia Co., Ltd.), the single-gloss bleached kraft paper (Oji F-Tex Co., Ltd.) A paper laminate was obtained in the same manner as in Example 2 except that a resin layer and a protective layer were formed on the surface (non-smooth surface) opposite to the smooth surface (manufactured by the company).
［実施例６］
実施例２の紙積層体の作製において、片艶晒クラフト紙（王子マテリア株式会社製）の平滑面の逆側の面（非平滑面）に代えて、片艶晒クラフト紙（王子エフテックス株式会社製）の平滑面（艶面）に樹脂層および保護層を形成した以外は、実施例２と同様にして紙積層体を得た。[Example 6]
In the production of the paper laminate of Example 2, instead of the surface opposite to the smooth surface (non-smooth surface) of the single-gloss bleached kraft paper (manufactured by Oji Materia Co., Ltd.), the single-gloss bleached kraft paper (Oji F-Tex Co., Ltd.) A paper laminate was obtained in the same manner as in Example 2 except that a resin layer and a protective layer were formed on the smooth surface (glossy surface) of (manufactured by the company).
[実施例７]
実施例４の紙積層体において、保護層の上にさらに、水性ヒートシール剤（主成分：変性ポリオレフィン樹脂）を６ｇ／ｍ２を塗工し、シーラント層（厚さ：６μｍ）を形成し、紙積層体を得た。[Example 7]
In the paper laminate of Example 4, 6 g / m 2 of an aqueous heat sealant (main component: modified polyolefin resin) was further applied onto the protective layer to form a sealant layer (thickness: 6 μm). A paper laminate was obtained.
[実施例８]
実施例５の紙積層体において、保護層の上にさらに、水性ヒートシール剤（主成分：変性ポリオレフィン樹脂）を６ｇ／ｍ２を塗工し、シーラント層（厚さ：６μｍ）を形成し、紙積層体を得た。[Example 8]
In the paper laminate of Example 5, 6 g / m 2 of an aqueous heat sealant (main component: modified polyolefin resin) was further applied onto the protective layer to form a sealant layer (thickness: 6 μm). A paper laminate was obtained.
［実施例９］
実施例１の紙積層体の作製において、片艶晒クラフト紙（王子マテリア株式会社製）の平滑面の逆側の面（非平滑面）に代えて、片艶未晒クラフト紙（天間特殊製紙株式会社製）の平滑面の逆側の面（非平滑面）に樹脂層および保護層を形成した以外は、実施例１と同様にして紙積層体を得た。紙基材として使用した片艶未晒クラフト紙は、坪量５０ｇ／ｍ２、厚さ６５μｍ、密度０．８０ｇ／ｃｍ３、平滑面の王研式平滑度２１３秒、非平滑面の王研式平滑度２５秒であった。[Example 9]
In the production of the paper laminate of Example 1, instead of the surface opposite to the smooth surface (non-smooth surface) of the single-gloss bleached kraft paper (manufactured by Oji Materia Co., Ltd.), the single-gloss unbleached kraft paper (Tenma Special) A paper laminate was obtained in the same manner as in Example 1 except that a resin layer and a protective layer were formed on the surface (non-smooth surface) opposite to the smooth surface (manufactured by Paper Manufacturing Co., Ltd.). The single-gloss unbleached kraft paper used as the paper base material has a basis weight of 50 g / m 2 , a thickness of 65 μm, a density of 0.80 g / cm 3 , a smooth surface of Oken-style smoothness of 213 seconds, and a non-smooth surface of Oken. The formula smoothness was 25 seconds.
［実施例１０］
実施例２の紙積層体の作製において、片艶晒クラフト紙（王子マテリア株式会社製）の平滑面の逆側の面（非平滑面）に代えて、片艶未晒クラフト紙（天間特殊製紙株式会社製）の平滑面の逆側の面（非平滑面）に樹脂層および保護層を形成した以外は、実施例２と同様にして紙積層体を得た。[Example 10]
In the production of the paper laminate of Example 2, instead of the surface opposite to the smooth surface (non-smooth surface) of the single-gloss bleached kraft paper (manufactured by Oji Materia Co., Ltd.), the single-gloss unbleached kraft paper (Tenma Special) A paper laminate was obtained in the same manner as in Example 2 except that a resin layer and a protective layer were formed on the surface (non-smooth surface) opposite to the smooth surface (manufactured by Paper Manufacturing Co., Ltd.).
［比較例１］
実施例１の紙積層体の作製において、片艶晒クラフト紙（王子マテリア株式会社製）に代えて、晒クラフト紙（王子マテリア株式会社製）を使用し、さらに晒クラフト紙の一方の面に樹脂層および保護層を形成した以外は、実施例１と同様にして紙積層体を得た。紙基材として使用した晒クラフト紙は、坪量５０ｇ／ｍ２、厚さ６０μｍ、密度０．７６ｇ／ｍ３、一方の面の王研式平滑度６３秒、他方の面の王研式平滑度４５秒であった。[Comparative Example 1]
In the production of the paper laminate of Example 1, bleached kraft paper (manufactured by Oji Materia Co., Ltd.) was used instead of the single-gloss bleached kraft paper (manufactured by Oji Materia Co., Ltd.), and further on one side of the bleached kraft paper. A paper laminate was obtained in the same manner as in Example 1 except that the resin layer and the protective layer were formed. The bleached kraft paper used as the paper substrate has a basis weight of 50 g / m 2 , a thickness of 60 μm, a density of 0.76 g / m 3 , a Oken-type smoothness on one side for 63 seconds, and a Oken-type smoothness on the other side. The degree was 45 seconds.
［比較例２］
実施例２の紙積層体の作製において、片艶晒クラフト紙（王子マテリア株式会社製）に代えて、晒クラフト紙（王子マテリア株式会社製）を使用し、さらに晒クラフト紙の一方の面に樹脂層および保護層を形成した以外は、実施例２と同様にして紙積層体を得た。紙基材として使用した晒クラフト紙は、坪量５０ｇ／ｍ２、厚さ６０μｍ、密度０．７６ｇ／ｍ３、一方の面の王研式平滑度６３秒、他方の面の王研式平滑度４５秒であった。[Comparative Example 2]
In the production of the paper laminate of Example 2, bleached kraft paper (manufactured by Oji Materia Co., Ltd.) was used instead of the single-gloss bleached kraft paper (manufactured by Oji Materia Co., Ltd.), and further on one side of the bleached kraft paper. A paper laminate was obtained in the same manner as in Example 2 except that the resin layer and the protective layer were formed. The bleached kraft paper used as the paper substrate has a basis weight of 50 g / m 2 , a thickness of 60 μm, a density of 0.76 g / m 3 , a Oken-type smoothness on one side for 63 seconds, and a Oken-type smoothness on the other side. The degree was 45 seconds.
［比較例３］
実施例１の紙積層体の作製において、樹脂層と保護層を形成せず、紙基材だけを評価に供した。[Comparative Example 3]
In the preparation of the paper laminate of Example 1, only the paper base material was used for evaluation without forming the resin layer and the protective layer.
［比較例４］
実施例１の紙積層体の作製において、片艶晒クラフト紙（王子マテリア株式会社製）に代えて、未晒クラフト紙（王子マテリア株式会社製）を使用し、さらに未晒クラフト紙の一方の面に樹脂層および保護層を形成した以外は、実施例１と同様にして紙積層体を得た。紙基材として使用した未晒クラフト紙は、坪量５０ｇ／ｍ２、厚さ７４μｍ、密度０．６８ｇ／ｃｍ３、一方の面の王研式平滑度１８秒、他方の面の王研式平滑度１７秒であった。[Comparative Example 4]
In the production of the paper laminate of Example 1, unbleached kraft paper (manufactured by Oji Materia Co., Ltd.) is used instead of the single-gloss bleached kraft paper (manufactured by Oji Materia Co., Ltd.), and one of the unbleached kraft papers is further produced. A paper laminate was obtained in the same manner as in Example 1 except that a resin layer and a protective layer were formed on the surface. The unbleached kraft paper used as the paper base material has a basis weight of 50 g / m 2 , a thickness of 74 μm, a density of 0.68 g / cm 3 , a Wangken type smoothness on one side of 18 seconds, and a Wangken type on the other side. The smoothness was 17 seconds.
得られた紙積層体および紙基材について、以下の各性能を評価した。評価結果は表１に示すとおりであった。 The following performances were evaluated for the obtained paper laminate and paper base material. The evaluation results are as shown in Table 1.
・水蒸気透過度
ＪＩＳ Ｚ０２０８：１９７６（カップ法）Ｂ法（温度４０℃±０．５℃、相対湿度９０％±２％）に準拠して、紙積層体の樹脂層が内側（低湿度側）に来るように配置して、水蒸気透過性を測定した。水蒸気透過度の値は低いほど水蒸気バリア性に優れる。-Moisture vapor transmission rate JIS Z0208: 1976 (cup method) B method (temperature 40 ° C ± 0.5 ° C, relative humidity 90% ± 2%), the resin layer of the paper laminate is inside (low humidity side) The water vapor permeability was measured by arranging so as to come to. The lower the value of water vapor transmission rate, the better the water vapor barrier property.
・酸素透過度
酸素透過率測定装置（ＭＯＣＯＮ社製、ＯＸ−ＴＲＡＮ２／２０）を使用し、大気圧下で温度２３℃、相対湿度５０％の条件（低湿度条件）にて、紙積層体の酸素透過度を測定した。酸素透過度の値は低いほど酸素バリア性に優れる。-Oxygen permeability Using an oxygen permeability measuring device (OX-TRAN2 / 20 manufactured by MOCON), the paper laminate was placed under atmospheric pressure at a temperature of 23 ° C and a relative humidity of 50% (low humidity condition). Oxygen permeability was measured. The lower the oxygen permeability value, the better the oxygen barrier property.
・離解率
得られた紙積層体をＪＩＳ Ｐ ８２２０：２０１２に準拠して離解した。このとき、離解開始から１０分後にスクリーン上の試料を回収して乾燥させることで残渣の質量比率（％）を算出し、１００−残渣の質量比率を離解率（％）とした。Dissociation rate The obtained paper laminate was dissociated in accordance with JIS P 8220: 2012. At this time, the mass ratio (%) of the residue was calculated by collecting and drying the sample on the screen 10 minutes after the start of dissociation, and the mass ratio of 100-residue was defined as the dissociation rate (%).
・印刷濃度
グラビア印刷適性試験機を用い、得られた紙積層体の樹脂層および保護層の非塗工面に対し、速度６０ｍ／ｍｉｎ、印圧４０ｋｇ／ｃｍでザーン粘度を１８秒に調製したグラビアインキの印刷を行った。このとき印刷が最も濃い領域に対して、ポータブル反射濃度計（Ｇｒｅｔａｇ Ｍａｃｂｅｔｈ ＲＤ−１９）を用いて印刷面の濃度の測定を行った。-Print density Gravure using a gravure printability tester to adjust the Zahn viscosity to 18 seconds at a speed of 60 m / min and a printing pressure of 40 kg / cm on the uncoated surfaces of the resin layer and protective layer of the obtained paper laminate. Ink was printed. At this time, the density of the printed surface was measured using a portable reflection density meter (Gretag Macbeth RD-19) for the region where the printing was the darkest.
・地合い
地合計（Ｍｋ ｓｙｓｔｅｍｓ社、３Ｄシートアナライザー）を使用し、得られた紙積層体の地合いの測定を行った。ＲＡＮＧＥを１に設定し、測定面は平滑度が高い方の面とした。-The texture of the obtained paper laminate was measured using the total texture (Mk systems, 3D sheet analyzer). RANGE was set to 1, and the measurement surface was the surface with higher smoothness.
・不透明度
ＪＩＳ Ｐ ８１４９：２０００に準じて、得られた紙積層体の不透明度の測定を行った。平滑度が高い方の面の不透明度を測定した。-Opacity The opacity of the obtained paper laminate was measured according to JIS P 8149: 2000. The opacity of the surface with the higher smoothness was measured.
表１では、紙基材として片艶晒クラフト紙を用いた実施例１〜８と、紙基材として王研式平滑度が１００秒以上の平滑面がない晒クラフト紙を用いた比較例１〜３とを比較した。
実施例１〜８の紙積層体は水蒸気透過度および酸素透過度が低く、さらに離解率が高かった。すなわち、実施例１〜８の紙積層体は離解性に優れ、高いバリア性を有していた。
一方、比較例１および２の紙積層体は、離解率が低く、離解性に劣っていた。
また、紙基材の少なくとも一方の面に樹脂層および保護層を有しない比較例３の紙積層体は、水蒸気透過度および酸素透過度が高く、バリア性に劣っていた。In Table 1, Examples 1 to 8 using single-gloss bleached kraft paper as the paper base material and Comparative Example 1 using Oken-type bleached kraft paper having a smoothness of 100 seconds or more and no smooth surface as the paper base material. Compared with ~ 3.
The paper laminates of Examples 1 to 8 had low water vapor transmission rate and oxygen permeability, and further had a high dissociation rate. That is, the paper laminates of Examples 1 to 8 were excellent in dissociation property and had high barrier property.
On the other hand, the paper laminates of Comparative Examples 1 and 2 had a low dissociation rate and were inferior in dissociation property.
Further, the paper laminate of Comparative Example 3 having no resin layer and protective layer on at least one surface of the paper base material had high water vapor transmission rate and oxygen permeability, and was inferior in barrier property.
表２では、紙基材として片艶未晒クラフト紙を用いた実施例９〜１０と、紙基材として王研式平滑度が１００秒以上の平滑面がない未晒クラフト紙を用いた比較例４とを比較した。
実施例９〜１０の紙積層体は水蒸気透過度および酸素透過度が低く、さらに離解率が高かった。すなわち、実施例９〜１０の紙積層体は離解性に優れ、高いバリア性を有していた。
一方、比較例４の紙積層体は、離解率が低く、離解性に劣っていた。さらに、比較例４の紙積層体は、水蒸気透過度が高く、水蒸気バリア性に劣っていた。
さらに、紙基材として片艶未晒クラフト紙を用いた実施例９〜１０は、片艶晒クラフト紙を用いた実施例１〜８よりも不透明度が高かった。そのため、実施例９〜１０の紙積層体は包装材料として用いた場合に中身が透けにくいという点でより優れていた。Table 2 shows a comparison between Examples 9 to 10 using single-gloss unbleached kraft paper as the paper base material and unbleached kraft paper having a smoothness of 100 seconds or more and no smooth surface as the paper base material. Comparison with Example 4.
The paper laminates of Examples 9 to 10 had low water vapor transmission rate and oxygen permeability, and further had a high dissociation rate. That is, the paper laminates of Examples 9 to 10 were excellent in dissociation property and had high barrier property.
On the other hand, the paper laminate of Comparative Example 4 had a low dissociation rate and was inferior in dissociation property. Further, the paper laminate of Comparative Example 4 had high water vapor transmission rate and was inferior in water vapor barrier property.
Further, Examples 9 to 10 using single-gloss unbleached kraft paper as the paper base material had higher opacity than Examples 1 to 8 using single-gloss bleached kraft paper. Therefore, the paper laminates of Examples 9 to 10 are more excellent in that the contents are difficult to see through when used as a packaging material.
Claims (14)
前記紙基材の密度が０．５０ｇ／ｃｍ３以上０．９０ｇ／ｃｍ３以下であり、
前記紙基材の片方の面が平滑面であり、
ＪＩＳ Ｐ ８１５５：２０１０に準拠して測定される、前記平滑面の王研式平滑度が１００秒以上であり、
前記樹脂層が水懸濁性高分子、アスペクト比が５０以上の板状無機化合物、およびカチオン性樹脂を含有し、
前記保護層が水溶性高分子を含有する、紙積層体。A paper laminate having a paper base material and a resin layer and a protective layer on at least one surface of the paper base material.
The density of the paper substrate is 0.50 g / cm 3 or more and 0.90 g / cm 3 or less.
One side of the paper substrate is a smooth surface,
The Oken-type smoothness of the smooth surface measured in accordance with JIS P 8155: 2010 is 100 seconds or more.
The resin layer contains a water-suspendable polymer, a plate-like inorganic compound having an aspect ratio of 50 or more, and a cationic resin.
A paper laminate in which the protective layer contains a water-soluble polymer.
The paper laminate according to any one of claims 1 to 13, which is a material for packaging.
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| JP2007216592A (en) * | 2006-02-20 | 2007-08-30 | Oji Paper Co Ltd | Gas barrier laminate |
| JP2014237309A (en) * | 2013-03-08 | 2014-12-18 | 日本製紙株式会社 | Paper-made barrier packaging material |
| WO2018062466A1 (en) * | 2016-09-30 | 2018-04-05 | 日本製紙株式会社 | Paper barrier material |
| JP2019108633A (en) * | 2017-12-20 | 2019-07-04 | 大王製紙株式会社 | Oil-resistant paper and method of producing the same |
| JP2020069783A (en) * | 2018-10-26 | 2020-05-07 | 王子ホールディングス株式会社 | Gas barrier laminate |
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| JP2007216592A (en) * | 2006-02-20 | 2007-08-30 | Oji Paper Co Ltd | Gas barrier laminate |
| JP2014237309A (en) * | 2013-03-08 | 2014-12-18 | 日本製紙株式会社 | Paper-made barrier packaging material |
| WO2018062466A1 (en) * | 2016-09-30 | 2018-04-05 | 日本製紙株式会社 | Paper barrier material |
| JP2019108633A (en) * | 2017-12-20 | 2019-07-04 | 大王製紙株式会社 | Oil-resistant paper and method of producing the same |
| JP2020069783A (en) * | 2018-10-26 | 2020-05-07 | 王子ホールディングス株式会社 | Gas barrier laminate |
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