JP5331265B1 - Paper barrier packaging material - Google Patents
Paper barrier packaging material Download PDFInfo
- Publication number
- JP5331265B1 JP5331265B1 JP2013505656A JP2013505656A JP5331265B1 JP 5331265 B1 JP5331265 B1 JP 5331265B1 JP 2013505656 A JP2013505656 A JP 2013505656A JP 2013505656 A JP2013505656 A JP 2013505656A JP 5331265 B1 JP5331265 B1 JP 5331265B1
- Authority
- JP
- Japan
- Prior art keywords
- barrier layer
- water vapor
- paper
- packaging material
- coating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 230000004888 barrier function Effects 0.000 title claims abstract description 313
- 239000005022 packaging material Substances 0.000 title claims abstract description 82
- 239000010410 layer Substances 0.000 claims abstract description 189
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 170
- 229920005989 resin Polymers 0.000 claims abstract description 46
- 239000011347 resin Substances 0.000 claims abstract description 46
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 239000011247 coating layer Substances 0.000 claims abstract description 21
- 239000011230 binding agent Substances 0.000 claims abstract description 18
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 13
- 239000011248 coating agent Substances 0.000 claims description 124
- 239000000123 paper Substances 0.000 claims description 123
- 238000000576 coating method Methods 0.000 claims description 116
- 239000000049 pigment Substances 0.000 claims description 78
- 239000002245 particle Substances 0.000 claims description 64
- 235000012211 aluminium silicate Nutrition 0.000 claims description 47
- 239000005995 Aluminium silicate Substances 0.000 claims description 46
- 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 46
- 239000000463 material Substances 0.000 claims description 25
- 239000003431 cross linking reagent Substances 0.000 claims description 24
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 19
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 18
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical group C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 18
- 239000002174 Styrene-butadiene Substances 0.000 claims description 16
- 239000011115 styrene butadiene Substances 0.000 claims description 16
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 16
- 239000000057 synthetic resin Substances 0.000 claims description 8
- 229920003002 synthetic resin Polymers 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000007900 aqueous suspension Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 11
- 239000007789 gas Substances 0.000 description 89
- 239000007788 liquid Substances 0.000 description 51
- 239000000243 solution Substances 0.000 description 22
- 239000007787 solid Substances 0.000 description 21
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 20
- 239000001301 oxygen Substances 0.000 description 20
- 229910052760 oxygen Inorganic materials 0.000 description 20
- 239000003795 chemical substances by application Substances 0.000 description 15
- 239000004816 latex Substances 0.000 description 14
- 229920000126 latex Polymers 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- -1 pH adjusters Substances 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 229910000019 calcium carbonate Inorganic materials 0.000 description 10
- 239000001023 inorganic pigment Substances 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 8
- 239000010445 mica Substances 0.000 description 8
- 229910052618 mica group Inorganic materials 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 235000011126 aluminium potassium sulphate Nutrition 0.000 description 7
- 239000004927 clay Substances 0.000 description 7
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 7
- 239000002270 dispersing agent Substances 0.000 description 7
- 229910052901 montmorillonite Inorganic materials 0.000 description 7
- 229940050271 potassium alum Drugs 0.000 description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002655 kraft paper Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229920001131 Pulp (paper) Polymers 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 229920002401 polyacrylamide Polymers 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 239000012860 organic pigment Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000002518 antifoaming agent Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000011121 hardwood Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 239000011122 softwood Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 150000001261 hydroxy acids Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 229940085991 phosphate ion Drugs 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
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- 239000011701 zinc Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
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- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
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- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
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- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
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- 239000000344 soap Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000004320 sodium erythorbate Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000013053 water resistant agent Substances 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/10—Packing paper
-
- 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
-
- 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
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained 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
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
-
- 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
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/60—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
-
- 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
-
- 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
- D21H19/822—Paper comprising more than one coating superposed two superposed coatings, both being pigmented
-
- 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/50—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by form
- D21H21/52—Additives of definite length or shape
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
- Packages (AREA)
- Wrappers (AREA)
- Laminated Bodies (AREA)
Abstract
紙基材上に水蒸気バリア層、該水蒸気バリア層上に形成されたガスバリア層を含む複数の塗工層が形成された紙製バリア包装材料であって、塗工層が水溶性高分子あるいは水中懸濁性性高分子をバインダー樹脂として用いて形成した塗工層である優れたガスバリア性と水蒸気バリア性を併せ持つ紙製バリア包装材料。 A paper barrier packaging material having a water vapor barrier layer formed on a paper substrate and a plurality of coated layers including a gas barrier layer formed on the water vapor barrier layer, wherein the coated layer is a water-soluble polymer or water A paper barrier packaging material having both excellent gas barrier properties and water vapor barrier properties, which is a coating layer formed using a suspending polymer as a binder resin.
Description
本発明は、食品の包装材又は容器やカップ等用いられる紙製バリア材料に関する。 BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a paper barrier material used for food packaging materials or containers, cups and the like.
紙製の包装材料にガスバリア性（特に、酸素バリア性）を付与することは、包装される各種製品をガスによる劣化、例えば酸素による酸化等から守るために重要である。 Providing gas barrier properties (in particular, oxygen barrier properties) to paper packaging materials is important for protecting various products to be packaged from deterioration by gas, such as oxidation with oxygen.
従来から、紙基材に金属箔やフィルムを積層したガスバリア性を付与した紙製の包装材料が提供されている。バリア層を形成する材料として、アルミニウム等の金属からなる金属箔や金属蒸着フィルム、ポリビニルアルコールやエチレン−ビニルアルコール共重合体、ポリ塩化ビニリデン、ポリアクリロニトリル等の樹脂フィルム、あるいはこれらの樹脂をコーティングしたフィルム、更に酸化珪素や酸化アルミニウム等の無機酸化物を蒸着したセラミック蒸着フィルム等がある。
上記以外に、ガスバリア性を付与した紙製の包装材料としては、水溶性高分子と無機層状化合物からなるガスバリア層を有する紙製のガスバリア材料が特許文献１、特許文献２に開示されている。被覆層上に特定のビニルアルコール系重合体からなるバリア層を設けた紙製のガスバリア材料が特許文献２に開示されている。
また、紙製の包装材料に耐水性（特に、水蒸気バリア性）を付与することも、包装される各種製品を水蒸気による劣化から守るために重要である。
紙基材上に水蒸気バリア性に優れる樹脂フィルム、あるいはこれらの水蒸気バリア性に優れる樹脂をコーティングしたフィルム等を紙基材に押し出しラミネート、又は、貼合する方法によって、水蒸気バリア性を付与した紙製包装材が提案されている。合成樹脂ラテックス、ワックス及び無機微粒子からなる防湿層を有する包装用紙が特許文献３に開示されている。
更に、紙製の包装材料にガスバリア性と水蒸気バリア性の両方を付与した包装材料としては、紙基材にガスバリア性を有する樹脂と水蒸気バリア性を有する樹脂をラミネートした包装材料が知られている。DESCRIPTION OF RELATED ART Conventionally, the paper-made packaging material which provided the gas-barrier property which laminated | stacked metal foil and a film on the paper base material is provided. As a material for forming the barrier layer, a metal foil or a metal-deposited film made of metal such as aluminum, a resin film such as polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyvinylidene chloride or polyacrylonitrile, or these resins are coated There are a film, a ceramic vapor deposition film in which an inorganic oxide such as silicon oxide or aluminum oxide is further vapor deposited, and the like.
In addition to the above, as a paper packaging material provided with gas barrier properties, Patent Documents 1 and 2 disclose a paper gas barrier material having a gas barrier layer composed of a water-soluble polymer and an inorganic layered compound. Patent Document 2 discloses a paper gas barrier material provided with a barrier layer composed of a specific vinyl alcohol polymer on a covering layer.
Also, imparting water resistance (in particular, water vapor barrier property) to paper packaging materials is also important for protecting various products to be packaged from deterioration by water vapor.
Paper with water vapor barrier property imparted by a method of extruding or laminating a resin film excellent in water vapor barrier property on a paper base material, or a film etc. coated with a resin excellent in these water vapor barrier properties on a paper base Packaging materials have been proposed. Patent Document 3 discloses a packaging sheet having a moisture-proof layer made of synthetic resin latex, wax and inorganic fine particles.
Furthermore, as a packaging material which gave both the gas barrier property and the water vapor barrier property to the paper packaging material, a packaging material obtained by laminating a resin having a gas barrier property and a resin having a water vapor barrier property on a paper substrate is known. .
紙基材(原紙)にガスバリア性を有する樹脂と水蒸気バリア性を有する樹脂を押し出しラミネートにより両バリア層形成した包装材料は、押し出しラミネート可能な樹脂の種類等に制限があるため、要求品質に対応できないといった問題があった。また、ガスバリア性と水蒸気バリア性を両立させるため、紙基材に多層ラミネートした包装材料は、紙やラミネート層をリサイクルすることが困難である。多層ラミネートした包装材料は、その製造におけるＣＯ2排出量が多くなるといった問題もある。更に、多層ラミネートの包装材料では、各ラミネート層間に特定の接着樹脂を使用することが必要な場合もあり、その製造は煩雑であるといった問題もある。
一方、ガスバリア性を有する樹脂、水蒸気バリア性を有する樹脂を紙基材にコーティングした包装材料は、使用できる樹脂の種類等の制限が少なく、様々な要求品質への対応は可能になる。しかしながら、ガスバリア性、水蒸気バリア性の両方を付与した包装材料、例えば、特許文献１あるいは特許文献２のガスバリア性を有す包装材料の上に特許文献３の防湿層を設けた場合、良好な水蒸気バリア性は得られるもののガスバリア性が得られなくなる問題があった。また、特許文献３の防湿層を有する防湿紙の上に特許文献１あるいは特許文献２のガスバリア層を設ける場合、防湿層の表面張力が低く、はじきによりガスバリア層が均一に形成されないため、十分なガスバリア性を得ることができなかった。A packaging material in which both barrier layers are formed by extruding and laminating a resin having gas barrier properties and a resin having water vapor barrier properties on a paper base material (base paper) has limitations on the types of resins that can be extruded and laminated. There was a problem that it was impossible. Moreover, in order to make gas barrier property and water vapor barrier property make compatible, it is difficult to recycle paper and a laminate layer in the packaging material laminated in multiple layers to the paper base material. Multilayer laminated packaging materials also have the problem of increased CO 2 emissions in their manufacture. Furthermore, in the packaging material of a multilayer laminate, it may be necessary to use a specific adhesive resin between each laminate layer, and there is also a problem that the manufacture is complicated.
On the other hand, a packaging material obtained by coating a paper substrate with a resin having gas barrier properties and a resin having water vapor barrier properties has few limitations such as the type of resin that can be used, and it becomes possible to cope with various required qualities. However, when the moisture-proof layer of Patent Document 3 is provided on a packaging material having both gas barrier properties and water vapor barrier properties, for example, the packaging material having gas barrier properties of Patent Document 1 or Patent Document 2, good water vapor Although barrier properties can be obtained, there is a problem that gas barrier properties can not be obtained. Further, when the gas barrier layer of Patent Document 1 or Patent Document 2 is provided on the moistureproof paper having the moistureproof layer of Patent Document 3, the surface tension of the moistureproof layer is low, and the gas barrier layer is not uniformly formed by repelling. Gas barrier properties could not be obtained.
そこで、本発明は、優れたガスバリア性と水蒸気バリア性を併せ持つ紙製バリア包装材料を提供すること目的とする。 Therefore, an object of the present invention is to provide a paper barrier packaging material having both excellent gas barrier properties and water vapor barrier properties.
本発明は、主な構成は次のとおりである。
１．紙基材上に複数の塗工層が設けられた紙製バリア包装材料であって、
該複数の塗工層が紙基材上に形成された水蒸気バリア層、該水蒸気バリア層上に形成されたガスバリア層を含んでおり、
これらの塗工層には、顔料を含み、バインダー樹脂として水溶性高分子あるいは水中懸濁性高分子が用いられており、
水蒸気バリア層には、前記顔料として、平均粒子径５μｍ以上、アスペクト比１０以上のカオリンが全顔料に対して５０〜１００重量％含有されており
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ことを特徴とする紙製バリア包装材料。
２．水蒸気バリア層およびガスバリア層は、異なる組成の塗工料であることを特徴とする１．に記載の紙製バリア包装材料。
３．水蒸気バリア層のバインダー樹脂は、スチレン・ブタジエン系合成樹脂であることを特徴とする１．又は２．に記載の紙製バリア包装材料。
４．水蒸気バリア層は平均粒子径５μｍ以下の顔料が含まれていることを特徴とする１．〜３．のいずれかに記載の紙製バリア包装材料。
５．水蒸気バリア層を形成する塗工料には架橋剤を含有していることを特徴とする１．〜４．のいずれかに記載の紙製バリア包装材料。
６．ガスバリア層は平均粒子径５μｍ以上且つアスペクト比１０以上のカオリンを含有することを特徴とする１．〜５．のいずれかに記載の紙製バリア包装材料。
７．ガスバリア層を形成する塗工料には架橋剤を含有していることを特徴とする１．〜６．のいずれかに記載の紙製バリア包装材料。
８．水蒸気バリア層の塗工量が乾燥重量で４〜３０ｇ／ｍ2、ガスバリア層の塗工量が乾燥重量で０．２〜１０ｇ／ｍ2であることを特徴とする１．〜７．のいずれかに記載の紙製バリア包装材料。
９．乾燥物用であることを特徴とする１．〜８．のいずれかに記載の紙製バリア包装材料。
The main configuration of the present invention is as follows.
1. A paper barrier packaging material having a plurality of coating layers provided on a paper substrate,
The plurality of coating layers include a water vapor barrier layer formed on a paper substrate, and a gas barrier layer formed on the water vapor barrier layer,
These coating layers comprises a pigment, a water-soluble polymer or water suspension of high molecules are used as a binder resin,
The water vapor barrier layer contains, as the pigment, 50 to 100% by weight of kaolin having an average particle diameter of 5 μm or more and an aspect ratio of 10 or more with respect to all the pigments.
The binder resin of the gas barrier layer is polyvinyl alcohol resin, and the paper barrier packaging material characterized by the above-mentioned.
2. The water vapor barrier layer and the gas barrier layer are coating agents of different compositions. Paper barrier packaging material as described in.
3. The binder resin of the water vapor barrier layer is a styrene-butadiene based synthetic resin. Or 2. Paper barrier packaging material as described in.
4. 1 water vapor barrier layer is characterized by that it contains the following pigment average particle size 5 [mu] m. ~ 3. The paper barrier packaging material as described in any of the above.
5. The coating agent for forming the water vapor barrier layer contains a crosslinking agent. ~ 4. The paper barrier packaging material as described in any of the above.
6. The gas barrier layer contains kaolin having an average particle diameter of 5 μm or more and an aspect ratio of 10 or more. To 5. The paper barrier packaging material as described in any of the above.
7. The coating agent for forming the gas barrier layer contains a crosslinking agent. ~ 6. The paper barrier packaging material as described in any of the above.
8. 1, wherein the coating amount of the water vapor barrier layer is 4~30g / m 2 on a dry weight coating amount of the gas barrier layer is 0.2 to 10 g / m 2 by dry weight. ~ 7. Paper barrier packaging materials fee according to any one of the.
9. It is characterized by being for dry matter. To 8. The paper barrier packaging material as described in any of the above.
（１）本発明は、紙基材の上に水蒸気バリア層、更にその上にガスバリア層の順に塗工によって形成することにより、水蒸気バリアとガスバリアの双方のバリア性を実現することができた。そして、バインダーとして水を分散媒とする高分子（水系塗料）を用いた塗工料塗工層によって水蒸気バリア層及びガスバリア層を形成することにより優れたガスバリア性と水蒸気バリア性を発揮する紙製バリア包装材料を提供することができる。
ガスバリア層と水蒸気バリア層を形成する塗工料は、乾燥固化してフィルム状となって水蒸気の透過及びガス（酸素）の透過を阻止する機能を発揮する。２種類のバリア層は水系塗料による塗工層は層間のなじみが良く、それぞれ他方から浸透し易い水蒸気あるいはガスによる界面の分離に対する抵抗が強く、両バリア機能を良好に維持できる。
（２）大粒径の顔料として平均粒子径５μｍ以上且つアスペクト比１０以上のカオリンを添加した塗工料を用いて水蒸気バリア層とガスバリア層の一方あるいは双方を形成することにより、水蒸気あるいはガスに対するバリア性が向上する。
（３）平均粒子径５μｍ以下の顔料を添加した塗工料を用いることによって、水蒸気あるいはガスに対するバリア性が向上する。
（４）水蒸気バリア層を形成する塗工層の高分子として、スチレン・ブタジエン系合成樹脂が適している。ガスバリア層を形成する塗工層の高分子として、ポリビニルアルコール樹脂が適している。紙基材の上にスチレン・ブタジエン系合成樹脂を主成分とする塗工層の上にポリビニルアルコール樹脂を主成分とする塗工層を形成する樹脂の組み合わせが、紙製バリア包装材料として優れている。
（５）架橋剤を添加したスチレン・ブタジエン系合成樹脂又はポリビニルアルコール樹脂は両バリア性を向上させる。(1) In the present invention, the barrier properties of both the water vapor barrier and the gas barrier can be realized by forming the water vapor barrier layer on the paper substrate and further forming the gas barrier layer thereon in this order. And a paper barrier that exhibits excellent gas barrier properties and water vapor barrier properties by forming a water vapor barrier layer and a gas barrier layer by a coating agent coating layer using a polymer (water-based paint) using water as a dispersion medium as a binder Packaging material can be provided.
The coating material for forming the gas barrier layer and the water vapor barrier layer is dried and solidified to be in the form of a film, and exhibits the function of blocking the permeation of water vapor and the permeation of gas (oxygen). In the two types of barrier layers, the coating layer of the water-based paint has good compatibility with the layers, resistance to separation of the interface by water vapor or gas which easily penetrates from the other is strong, and both barrier functions can be maintained well.
(2) A barrier against water vapor or gas by forming one or both of a water vapor barrier layer and a gas barrier layer using a coating material to which kaolin having an average particle diameter of 5 μm or more and an aspect ratio of 10 or more is added as a large particle diameter pigment. Improves the quality.
(3) By using a coating agent to which a pigment having an average particle diameter of 5 μm or less is added, the barrier property to water vapor or gas is improved.
(4) As a polymer of the coating layer which forms a water vapor barrier layer, a styrene butadiene type synthetic resin is suitable. Polyvinyl alcohol resin is suitable as a polymer of the coating layer which forms a gas barrier layer. A combination of resins forming a coating layer containing polyvinyl alcohol resin as a main component on a coating layer containing styrene / butadiene synthetic resin as a main component on a paper base is excellent as a paper barrier packaging material. There is.
(5) A styrene butadiene type synthetic resin or polyvinyl alcohol resin to which a crosslinking agent is added improves both barrier properties.
本発明は、紙基材上（以下、「原紙」ということがある。）に水蒸気バリア層、ガスバリア層をこの順に設けた紙製バリア包装材料（以下、「包装材料」ということがある。）である。二種類のバリア層は水性の塗工料を塗布して形成され、塗工料には、高分子バインダーを主として顔料、架橋剤等が添加されている。
水蒸気バリア層あるいはガスバリア層は水を分散媒とする高分子をバインダー樹脂として含む塗工料を用いて塗工によって形成される。この２種類のバリア層を形成する塗工層には、平均粒子径５μｍ以上且つアスペクト比１０以上のカオリン、平均粒子径５μｍ以下の顔料、架橋剤等を添加することが好ましい。In the present invention, a paper barrier packaging material (hereinafter sometimes referred to as "packaging material") in which a water vapor barrier layer and a gas barrier layer are provided in this order on a paper substrate (hereinafter sometimes referred to as "base paper"). It is. The two types of barrier layers are formed by applying an aqueous coating agent, and a pigment, a crosslinking agent and the like are mainly added to the polymer binder in the coating agent.
The water vapor barrier layer or the gas barrier layer is formed by coating using a coating agent containing a polymer containing water as a dispersion medium as a binder resin. It is preferable to add kaolin having an average particle diameter of 5 μm or more and an aspect ratio of 10 or more, a pigment having an average particle diameter of 5 μm or less, a crosslinking agent, or the like to the coating layer forming the two types of barrier layers.
紙基材の上に水蒸気バリア層、更にその上にガスバリア層を形成した本発明の紙製バリア包装材料が優れた水蒸気バリア性及びガスバリア性を併せ持つ理由は次のように推測される。
ガスバリア層の形成に水溶性高分子樹脂が用いられている例が多い。紙基材上にガスバリア層、水蒸気バリア層をこの順に設けた場合、紙基材を経由して浸透する空気中の水分等が作用して、水溶性高分子を含有するガスバリア層が劣化する。一方、紙基材上に、耐水性の良好な樹脂を含有する水蒸気バリア層、ガスバリア層をこの順に設けた場合、紙基材を経由した水分は水蒸気バリア層にブロックされるのでガスバリア層への影響（劣化）を防止することができる。このため、本発明の紙製バリア包装材料は良好な水蒸気バリア性及びガスバリア性を有する。
本発明の紙製バリア包装材料は、ガスバリア層側が内容物(被包装材)側で紙層側が外気側(外表面)として通常使用される。外気の水分が内部へ浸透することを防止できるので、被包装物が乾燥性の物質であれば、本発明の構造が有効である。湿った物を包装する場合は、更に、内側となるガスバリア層上に樹脂の押し出しラミネート層やフィルムのラミネート層を付加形成する。The reason why the paper barrier packaging material of the present invention, in which a water vapor barrier layer is formed on a paper substrate and a gas barrier layer is formed thereon, has both excellent water vapor barrier properties and gas barrier properties is presumed as follows.
In many cases, a water-soluble polymer resin is used to form the gas barrier layer. When the gas barrier layer and the water vapor barrier layer are provided in this order on the paper substrate, moisture and the like in the air which permeates through the paper substrate act to degrade the gas barrier layer containing the water-soluble polymer. On the other hand, when a water vapor barrier layer containing a resin having good water resistance and a gas barrier layer are provided in this order on a paper substrate, the water passing through the paper substrate is blocked by the water vapor barrier layer, so Influence (deterioration) can be prevented. For this reason, the paper barrier packaging material of the present invention has good water vapor barrier properties and gas barrier properties.
The paper barrier packaging material of the present invention is generally used with the gas barrier layer side as the content (wrapped material) side and the paper layer side as the open air side (outside surface). The structure of the present invention is effective if the material to be packaged is a dry substance, since it is possible to prevent the penetration of moisture from the outside into the interior. In the case of packaging a wet material, an extrusion laminate layer of a resin or a laminate layer of a film is additionally formed on the inner gas barrier layer.
＜紙基材について＞
本発明において紙基材とは、パルプ、填料、各種助剤からなるシートである。パルプとしては、広葉樹漂白クラフトパルプ(ＬＢＫＰ)、針葉樹漂白クラフトパルプ(ＮＢＫＰ)、サルファイトパルプ等の化学パルプ、ストーングラインドパルプ、サーモメカニカルパルプ等の機械パルプ、ケナフ、竹、麻等から得られた非木材繊維等である。これらの素材を適宜配合して用いることが可能である。これらの中でも、広葉樹漂白クラフトパルプ(ＬＢＫＰ)、針葉樹漂白クラフトパルプ(ＮＢＫＰ)等の化学パルプが好ましい。化学パルプは、原紙中への異物混入が発生し難いこと、使用後の紙容器を古紙原料に供してリサイクル使用する際に経時変色が発生し難いこと、高い白色度を有するため印刷時の面感が良好であり包装材料として使用価値が高くなること、等の理由から適している。<About paper base>
In the present invention, the paper base is a sheet composed of pulp, filler and various auxiliary agents. The pulp is obtained from chemical pulp such as hardwood bleached kraft pulp (LBKP), softwood bleached kraft pulp (NBKP), sulfite pulp etc., mechanical grind such as stone grind pulp, thermomechanical pulp, kenaf, bamboo, hemp etc. Non-wood fiber etc. It is possible to use these materials appropriately blended. Among these, chemical pulps such as hardwood bleached kraft pulp (LBKP) and softwood bleached kraft pulp (NBKP) are preferable. Chemical pulp is less likely to be contaminated with foreign matter in the base paper, less likely to undergo discoloration over time when used as a waste paper raw material and used as a paper container, and has a high whiteness, so it has a surface during printing Suitable for reasons such as good feeling and high value of use as packaging material.
填料としては、ホワイトカーボン、タルク、カオリン、クレー、重質炭酸カルシウム、軽質炭酸カルシウム、酸化チタン、ゼオライト、合成樹脂填料等の公知の填料を使用することができる。また、硫酸バンドや各種のアニオン性、カチオン性、ノニオン性あるいは、両性の歩留まり向上剤、濾水性向上剤、紙力増強剤や内添サイズ剤等の抄紙用内添助剤を必要に応じて使用することができる。更に、染料、蛍光増白剤、ｐＨ調整剤、消泡剤、ピッチコントロール剤、スライムコントロール剤等も必要に応じて添加することができる。 As the filler, known fillers such as white carbon, talc, kaolin, clay, ground calcium carbonate, light calcium carbonate, titanium oxide, zeolite, synthetic resin filler and the like can be used. In addition, internal additives for paper making such as sulfuric acid bands and various anionic, cationic, nonionic or amphoteric retention improvers, freeness improvers, paper strength improvers and internal sizing agents as needed It can be used. Furthermore, dyes, fluorescent whitening agents, pH adjusters, antifoaming agents, pitch control agents, slime control agents and the like can be added as necessary.
紙基材の製造（抄紙）方法は特に限定されるものではなく、公知の長網フォーマー、オントップハイブリッドフォーマー、ギャップフォーマーマシンを用いて、酸性抄紙、中性抄紙、アルカリ抄紙方式で抄紙して紙基材を製造することができる。また、紙基材は一般に塗工紙に用いられる坪量２５〜４００ｇ／ｍ2程度のものが好ましい。更に、紙基材の表面を各種薬剤で処理することが可能である。使用される薬剤としては、酸化澱粉、ヒドロキシエチルエーテル化澱粉、酸素変性澱粉、ポリアクリルアミド、ポリビニルアルコール、表面サイズ剤、耐水化剤、保水剤、増粘剤、滑剤等を例示することができ、これらを単独あるいは２種類以上を混合して用いることができる。紙基材の表面処理の方法は特に限定されるものではないが、ロッドメタリング式サイズプレス、ポンド式サイズプレス、ゲートロースコーター、スプレーコーター、ブレードコーター、カーテンコーター等公知の塗工装置を用いることができる。The method for producing the paper substrate (paper making) is not particularly limited, and it is possible to use the known long screen former, on-top hybrid former, gap former machine, acid paper making, neutral paper making, alkaline paper making Thus, a paper substrate can be produced. The paper substrate is preferably one having a basis weight of about 25 to 400 g / m 2 generally used for coated paper. Furthermore, it is possible to treat the surface of the paper substrate with various agents. Examples of the agent to be used include oxidized starch, hydroxyethyl etherified starch, oxygen modified starch, polyacrylamide, polyvinyl alcohol, surface sizing agent, water resistant agent, water retention agent, thickener, lubricant and the like, These can be used individually or in mixture of 2 or more types. Although the method of surface treatment of the paper substrate is not particularly limited, a known coating apparatus such as a rod metering size press, a pound size press, a gating oven, a spray coater, a blade coater, a curtain coater, etc. is used. be able to.
＜バインダー（高分子）について＞
水蒸気バリア層あるいはガスバリア層を形成する塗工層の主成分として用いる高分子は、水を分散媒として使用することができる樹脂が適している。剤型として、高分子水溶液あるいはエマルジョンの形態が含まれる。この高分子は塗工層を形成する塗工料のバインダーに該当する。<About binder (polymer)>
As the polymer used as the main component of the coating layer forming the water vapor barrier layer or the gas barrier layer, a resin which can use water as a dispersion medium is suitable. The dosage form includes the form of an aqueous polymer solution or an emulsion. This polymer corresponds to the binder of the coating material which forms a coating layer.
＜水蒸気バリア層について＞
水蒸気バリア層に含有させる樹脂としては、スチレン・ブタジエン系、スチレン・アクリル系、エチレン・酢酸ビニル系、ブタジエン・メチルメタクリレート系、酢酸ビニル・ブチルアクリレート系等の各種共重合体、無水マレイン酸共重合体、アクリル酸・メチルメタクリレート系共重合体等を単独あるいは２種類以上混合して使用することができる。これらの中ではスチレン・ブタジエン系樹脂が水蒸気バリア性の点から好ましい。
本発明においてスチレン・ブタジエン系合成樹脂とは、スチレンとブタジエンを主構成モノマーとし、これに変性を目的とする各種のコモノマーを組み合わせ、乳化重合したものである。コモノマーの例として、メチルメタクリルレート、アクリロニトリル、アクリルアミド、ヒドロキシエチルアクリレートや、イタコン酸、マレイン酸、アクリル酸等の不飽和カルボン酸等が挙げられる。
樹脂は、水を分散剤とし、乳化したエマルジョンタイプの塗工料として使用する。乳化剤としては、オレイン酸ナトリウム、ロジン酸石鹸、アルキルアリルスルホン酸ナトリウム、ジアルキルスルホコハク酸ナトリウム等のアニオン性界面活性剤である。これらを単独、又はノニオン性界面活性剤と組み合わせて用いることができる。更に、必要に応じて両性又はカチオン性界面活性剤を用いても良い。
本発明では、水蒸気バリア層を形成する塗工料には炭化水素、シリコーン系樹脂、フッ素系樹脂、脂肪酸及び脂肪酸とアルコールのエステル等の撥水成分を含有していないことが好ましい。なお、従来の水蒸気バリア性を有する包装材料は、撥水成分を含有した樹脂を設けてあることが一般的である。撥水成分は水蒸気バリア層とガスバリア層との親和性を低下することとなり、一方の層から浸透した水分やガスが界面剥離を促すこととなり、好ましくない。About the water vapor barrier layer
As the resin to be contained in the water vapor barrier layer, various copolymers such as styrene / butadiene type, styrene / acrylic type, ethylene / vinyl acetate type, butadiene / methyl methacrylate type, vinyl acetate / butyl acrylate type, maleic anhydride copolymer It is possible to use a combination, an acrylic acid / methyl methacrylate copolymer, etc. singly or in combination of two or more. Among these, styrene-butadiene resins are preferable from the viewpoint of water vapor barrier properties.
In the present invention, the styrene-butadiene based synthetic resin is obtained by emulsion polymerization of styrene and butadiene as main constituent monomers, in combination with various comonomers for the purpose of modification. Examples of the comonomer include methyl methacrylate, acrylonitrile, acrylamide, hydroxyethyl acrylate, and unsaturated carboxylic acids such as itaconic acid, maleic acid and acrylic acid.
The resin uses water as a dispersant and is used as an emulsified emulsion-type coating agent. The emulsifier is an anionic surfactant such as sodium oleate, rosin acid soap, sodium alkylaryl sulfonate, sodium dialkyl sulfosuccinate and the like. These can be used alone or in combination with a nonionic surfactant. Furthermore, if necessary, amphoteric or cationic surfactants may be used.
In the present invention, the coating material for forming the water vapor barrier layer preferably does not contain a water repellent component such as hydrocarbon, silicone resin, fluorine resin, fatty acid and ester of fatty acid and alcohol. In addition, it is general that the packaging material which has the conventional water-vapor-barrier property is provided with resin containing a water-repellent component. The water repellent component lowers the affinity between the water vapor barrier layer and the gas barrier layer, and the water or gas permeated from one layer promotes interfacial peeling, which is not preferable.
（水蒸気バリア層添加用顔料について）
本発明において、水蒸気バリア層に顔料を含有させることは、水蒸気バリア性を向上させる。また、水蒸気バリア層とガスバリア層の密着性が向上する。
顔料としては、無機顔料、有機顔料がある。無機顔料は、カオリン、クレー、エンジニアードカオリン、デラミネーテッドクレー、重質炭酸カルシウム、軽質炭酸カルシウム、タルク、二酸化チタン、硫酸バリウム、硫酸カルシウム、酸化亜鉛、珪酸、珪酸塩、コロイダルシリカ、サチンホワイト等である。有機顔料は、密実型、中空型、又はコアーシェル型等である。これらの顔料を単独又は２種類以上混合して使用することができる。
顔料は、扁平形状で大きなものが適している。更に、大粒径と小粒径を併用することにより水蒸気バリア性が向上する。
これらの顔料の中でも、形状が扁平なカオリン等の無機顔料は、水蒸気のバリア性を向上させる。特に、平均粒子径５μｍ以上且つアスペクト比１０以上のカオリンがより好ましい。扁平な顔料は塗工層に平行に分布し、水蒸気バリア層内に浸透した水蒸気は、扁平な顔料によって厚さ方向に移動することが遮られ、迂回して移動することとなり、水蒸気が水蒸気バリア層を通過する経路が長くなり、バリア性が向上する。添加する顔料のアスペクト比が小さいと塗工層中を水蒸気が迂回する回数が減少し、移動する距離が短くなるため、結果として水蒸気バリア性は、扁平で大粒径の顔料よりも劣ることとなる。
扁平な顔料は、ガスバリア層でも同様の作用が期待できる。
扁平な顔料として、カオリンの他、マイカやモンモリロナイトを使用することも可能である。しかしながら、マイカ、モンモリロナイトの分散液はカオリンの分散液より低濃度であり、マイカ、モンモリロナイトを用いた水蒸気バリア層用の塗工液は低濃度となるため、形成される水蒸気バリア層中でおいて、顔料が配向しにくくなるため、カオリンの方が適している。(About the pigment for steam barrier layer addition)
In the present invention, containing a pigment in the water vapor barrier layer improves the water vapor barrier properties. In addition, the adhesion between the water vapor barrier layer and the gas barrier layer is improved.
The pigments include inorganic pigments and organic pigments. Inorganic pigments include kaolin, clay, engineered kaolin, delaminated clay, calcium carbonate, light calcium carbonate, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silica, silicate, colloidal silica, satin white Etc. The organic pigment is a solid-solid type, a hollow type, or a core-shell type. These pigments can be used alone or in combination of two or more.
The pigment is suitably flat and large. Further, the combined use of the large particle size and the small particle size improves the water vapor barrier property.
Among these pigments, inorganic pigments such as kaolin having a flat shape improve the barrier property of water vapor. In particular, kaolin having an average particle diameter of 5 μm or more and an aspect ratio of 10 or more is more preferable. The flat pigment is distributed in parallel to the coating layer, and the water vapor that has penetrated into the water vapor barrier layer is blocked from moving in the thickness direction by the flat pigment and is diverted to move, and the water vapor is a water vapor barrier The path through the layer is lengthened and barrier properties are improved. When the aspect ratio of the pigment to be added is small, the number of times water vapor bypasses in the coating layer is reduced, and the distance of movement is shortened. As a result, the water vapor barrier property is inferior to flat and large particle size pigments. Become.
The flat pigment can be expected to have the same function even in the gas barrier layer.
As flat pigments, it is also possible to use mica or montmorillonite other than kaolin. However, since the dispersion of mica and montmorillonite has a lower concentration than the dispersion of kaolin, and the coating solution for a water vapor barrier layer using mica and montmorillonite has a low concentration, the dispersion is formed in the water vapor barrier layer to be formed. Because kaolin is difficult to orient, kaolin is more suitable.
水蒸気バリア層に上記した扁平な顔料添加に加えて平均粒子径が５μｍ以下の顔料を更に添加することにより、水蒸気バリア性を更に向上させることができる。この小粒径の顔料は扁平である必要はない。
本発明において、水蒸気バリア性の向上、及びガスバリア層との密着性の点から、平均粒子径５μｍ以上且つアスペクト比１０以上のカオリンを含有する水蒸気バリア層に、更に平均粒子径５μｍ以下の顔料を含有させることが好ましい。重層的に存在する均粒子径５μｍ以上且つアスペクト比１０以上のカオリンの間に平均粒子径５μｍ以下の顔料が入り込む構造となって、扁平なカオリンの面に沿って移動を余儀なくされる水蒸気は、この小さな顔料粒子により移動が阻止されることとなる。つまり、水蒸気バリア層に扁平性と平均粒子径の異なる顔料を含有させた場合、水蒸気バリア層中で、隣接する扁平で大きな粒子径の顔料の間に形成される空隙に小さな粒子径の顔料が充填された状態となり、水蒸気は顔料を迂回して通過するため、小さな粒子径の顔料を混入していない水蒸気バリア層と比較して、高い水蒸気バリア性を発揮する。The water vapor barrier property can be further improved by further adding a pigment having an average particle diameter of 5 μm or less to the water vapor barrier layer in addition to the flat pigment addition described above. The small particle size pigment need not be flat.
In the present invention, a pigment having an average particle diameter of 5 μm or less is further added to a water vapor barrier layer containing kaolin having an average particle diameter of 5 μm or more and an aspect ratio of 10 or more from the viewpoint of improvement of water vapor barrier properties and adhesion to a gas barrier layer. It is preferable to contain it. A pigment having an average particle diameter of 5 μm or less enters between kaolins having an average particle diameter of 5 μm or more and an aspect ratio of 10 or more, and water vapor forced to move along the flat kaolin surface is The small pigment particles will block migration. That is, when the water vapor barrier layer contains pigments having different flatness and average particle diameter, the pigment of small particle diameter is formed in the voids formed between the adjacent flat large particle diameter pigments in the water vapor barrier layer. In the state of being filled, the water vapor bypasses the pigment and passes it, so it exhibits high water vapor barrier properties as compared with the water vapor barrier layer not containing the pigment of small particle diameter.
本発明において、平均粒子径５μｍ以上且つアスペクト比１０以上のカオリンと平均粒子径５μｍ以下の顔料の配合比率が乾燥重量で、５０／５０〜９９／１であることが好ましい。平均粒子径５μｍ以上且つアスペクト比１０以上のカオリンの比率が上記範囲より少ないと水蒸気が塗工層中を迂回する距離が短くなるため、十分な水蒸気バリア性を得ることができない。一方、上記範囲より多いと、塗工層中の大粒径顔料が形成する空隙を平均粒子径５μｍ以下の顔料で十分に埋めることができないため、水蒸気バリア性の向上は見られない。
本発明において、平均粒子径５μｍ以下の顔料としてはカオリン、クレー、エンジニアードカオリン、デラミネーテッドクレー、重質炭酸カルシウム、軽質炭酸カルシウム、タルク、二酸化チタン、硫酸バリウム、硫酸カルシウム、酸化亜鉛、珪酸、珪酸塩、コロイダルシリカ、サチンホワイト等の無機顔料及び密実型、中空型、又はコアーシェル型等の有機顔料等を単独又は２種類以上混合して使用することができる。これらの顔料の中では、重質炭酸カルシウムが好ましい。In the present invention, the blending ratio of kaolin having an average particle diameter of 5 μm or more and an aspect ratio of 10 or more and a pigment having an average particle diameter of 5 μm or less is preferably 50/50 to 99/1 in dry weight. If the ratio of kaolin having an average particle diameter of 5 μm or more and an aspect ratio of 10 or more is smaller than the above range, the distance for water vapor to bypass in the coating layer becomes short, and sufficient water vapor barrier properties can not be obtained. On the other hand, when the content is more than the above range, the voids formed by the large particle diameter pigment in the coating layer can not be sufficiently filled with the pigment having an average particle diameter of 5 μm or less, and thus the water vapor barrier property is not improved.
In the present invention, as pigments having an average particle size of 5 μm or less, kaolin, clay, engineered kaolin, delaminated clay, ground calcium carbonate, light calcium carbonate, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid Inorganic pigments such as silicate, colloidal silica and satin white and organic pigments such as solid type, hollow type or core-shell type can be used singly or in combination of two or more. Among these pigments, ground calcium carbonate is preferred.
水蒸気バリア層に顔料を含有させる場合、樹脂と顔料の配合量は、顔料（乾燥重量）１００重量部に対して、樹脂（乾燥重量）５〜２００重量部の範囲で使用されることが好ましく、より好ましくは樹脂２０〜１５０重量部である。また、水蒸気バリア層には、樹脂、顔料の他、分散剤、増粘剤、保水剤、消泡剤、耐水化剤、染料、蛍光染料等の通常使用される各種助剤を使用することができる。 When a pigment is contained in the water vapor barrier layer, the compounding amount of the resin and the pigment is preferably used in the range of 5 to 200 parts by weight of the resin (dry weight) with respect to 100 parts by weight of the pigment (dry weight) More preferably, it is 20 to 150 parts by weight of resin. Further, in the water vapor barrier layer, in addition to resins and pigments, various commonly used auxiliary agents such as dispersants, thickeners, water retention agents, antifoaming agents, water resistance agents, dyes, fluorescent dyes, etc. may be used. it can.
（架橋剤）
本発明において、水蒸気バリア層に多価金属塩等に代表される架橋剤を添加することが好ましい。架橋剤は水蒸気バリア層に含有されるバインダーと架橋反応を起こすため、水蒸気バリア層内の結合の数（架橋点）が増加する。つまり、水蒸気バリア層が緻密な構造となり、良好な水蒸気バリア性を発揮する。(Crosslinking agent)
In the present invention, it is preferable to add a crosslinking agent represented by a polyvalent metal salt or the like to the water vapor barrier layer. The crosslinking agent causes a crosslinking reaction with the binder contained in the water vapor barrier layer, thereby increasing the number of bonds (crosslinking point) in the water vapor barrier layer. That is, the water vapor barrier layer has a dense structure, and exhibits good water vapor barrier properties.
本発明において、架橋剤の種類としては特に限定されるものではなく、水蒸気バリア層に含有されるバインダーの種類に合わせて、多価金属塩（銅、亜鉛、銀、鉄、カリウム、ナトリウム、ジルコニウム、アルミニウム、カルシウム、バリウム、マグネシウム、チタン等の多価金属と、炭酸イオン、硫酸イオン、硝酸イオン、燐酸イオン、珪酸イオン、窒素酸化物、ホウ素酸化物等のイオン性物質が結合した化合物）、アミン化合物、アミド化合物、アルデヒド化合物、ヒドロキシ酸等から適宜選択して使用することができる。架橋剤の配合部数は、塗工可能な塗料濃度や塗料粘度の範囲内であれば特に限定されることなく配合することができる。なお、水蒸気バリア性に優れた効果を発揮するスチレン・ブタジエン系、スチレン・アクリル系等のスチレン系の水蒸気バリア性樹脂を用いた場合、架橋効果発現の観点から、多価金属塩を使用することが好ましい。更に、カリウムミョウバンがより好ましい。
架橋剤の添加量は、水蒸気バリア層に使用されるバインダー樹脂１００重量部に対して、１〜１０重量部である。より好ましくは３〜５重量部である。１重量部より少ないと、十分な効果が得られず、１０重量部より多いと、塗工液の粘度が著しく増加するため、塗工困難になる。In the present invention, the kind of the crosslinking agent is not particularly limited, and a polyvalent metal salt (copper, zinc, silver, iron, potassium, sodium, zirconium) according to the kind of the binder contained in the water vapor barrier layer A compound in which a polyvalent metal such as aluminum, calcium, barium, magnesium, titanium, etc. and an ionic substance such as carbonate ion, sulfate ion, nitrate ion, phosphate ion, silicate ion, nitrogen oxide, boron oxide etc. An amine compound, an amide compound, an aldehyde compound, a hydroxy acid and the like can be appropriately selected and used. The number of blending parts of the crosslinking agent can be blended without being particularly limited as long as it is within the range of the paint concentration and the paint viscosity which can be applied. In the case of using a styrene-butadiene-based or styrene-acrylic-based water-vapor barrier resin that exhibits excellent effects of water-vapor barrier properties, polyvalent metal salts should be used from the viewpoint of the crosslinking effect. Is preferred. Furthermore, potassium alum is more preferred.
The addition amount of the crosslinking agent is 1 to 10 parts by weight with respect to 100 parts by weight of the binder resin used for the water vapor barrier layer. More preferably, it is 3 to 5 parts by weight. If the amount is less than 1 part by weight, a sufficient effect can not be obtained, and if the amount is more than 10 parts by weight, the viscosity of the coating liquid significantly increases, which makes coating difficult.
本発明において、水蒸気バリア層を形成させる塗工液に架橋剤を添加する場合、水酸化アンモニウム溶液等の極性溶媒に架橋剤を溶解させてから塗工液へ添加することが好ましい。架橋剤を極性溶媒に溶解することにより、架橋剤と極性溶媒で結合を作るため塗工液へ配合しても直ちにラテックスとの架橋反応は起こらず、塗料の増粘を抑制することができる。その場合、紙への塗工後に乾燥することにより極性溶媒成分が揮発し、バインダーとの架橋反応が起こり、緻密な水蒸気バリア層が形成されると推測される。 In the present invention, when a crosslinking agent is added to a coating liquid for forming a water vapor barrier layer, it is preferable to dissolve the crosslinking agent in a polar solvent such as an ammonium hydroxide solution and then add it to the coating liquid. By dissolving the crosslinking agent in the polar solvent, the crosslinking reaction with the polar solvent does not occur immediately even if it is incorporated in the coating liquid, so that the crosslinking reaction with the latex does not occur, and the thickening of the coating can be suppressed. In that case, it is presumed that the polar solvent component is volatilized by drying after coating on paper, a crosslinking reaction with the binder occurs, and a dense water vapor barrier layer is formed.
（接触角）
本発明において、紙基材上に設ける水蒸気バリア層表面の水との接触角は、９０°未満が好ましく、より好ましくは８５°未満、更に好ましくは８０°未満である。水との接触角が９０°以上であると、水蒸気バリア層上に均一なガスバリア層を設けることが困難となり、高いガスバリア性を発揮することが困難となる。９０°未満の場合には、水蒸気バリア層とガスバリア層の反発性を抑えて両層間の剥離を抑制することできる。この接触角は水蒸気バリア層とガスバリア層の親和性を推測する目安となる。
なお、水蒸気バリア層表面の水との接触角を調整する方法としては、限定されるものではないが、水との接触角の低い水蒸気バリア層用の樹脂の使用、顔料の添加等を挙げることができる。(Contact angle)
In the present invention, the contact angle with water of the surface of the water vapor barrier layer provided on the paper substrate is preferably less than 90 °, more preferably less than 85 °, still more preferably less than 80 °. When the contact angle with water is 90 ° or more, it becomes difficult to provide a uniform gas barrier layer on the water vapor barrier layer, and it becomes difficult to exhibit high gas barrier properties. If the angle is less than 90 °, the repulsion between the water vapor barrier layer and the gas barrier layer can be suppressed to suppress peeling between the two layers. The contact angle is a standard for estimating the affinity between the water vapor barrier layer and the gas barrier layer.
The method of adjusting the contact angle with water on the surface of the water vapor barrier layer is not limited, but mention may be made of the use of a resin for water vapor barrier layer with a low contact angle with water, addition of a pigment, etc. Can.
＜ガスバリア層について＞
本発明において、ガスバリア層を形成する塗工料のバインダー樹脂として使用される水溶性高分子としては、完全ケン化ポリビニルアルコール、部分ケン化ポリビニルアルコール、エチレン共重合ポリビニルアルコール、ポリビニルピロリドン、デンプン、メチルセルロース、カルボキシメチルセルロース、アルギン酸ナトリウム等を例示することができる。これらの中では、ガスバリア性の点から、ポリビニルアルコール、カルボキシメチルセルロースが好ましく、ポリビニルアルコールが更に好ましい。<About the gas barrier layer>
In the present invention, as the water-soluble polymer used as a binder resin of a coating material for forming a gas barrier layer, completely saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, ethylene copolymerized polyvinyl alcohol, polyvinyl pyrrolidone, starch, methyl cellulose, Carboxymethylcellulose, sodium alginate and the like can be exemplified. Among these, polyvinyl alcohol and carboxymethyl cellulose are preferable, and polyvinyl alcohol is more preferable, from the viewpoint of gas barrier properties.
（顔料について）
本発明において、ガスバリア層に使用される顔料としてはカオリン、クレー、エンジニアードカオリン、デラミネーテッドクレー、重質炭酸カルシウム、軽質炭酸カルシウム、タルク、二酸化チタン、硫酸バリウム、硫酸カルシウム、酸化亜鉛、珪酸、珪酸塩、コロイダルシリカ、サチンホワイト、マイカ等の無機顔料及び密実型、中空型、又はコアーシェル型等の有機顔料がある。これらを単独又は２種類以上混合して使用することができる。これらの中では、ガスバリア性の点から無機顔料を使用することが好ましい。
平均粒子径３μｍ以上、且つアスペクト比が１０以上の無機顔料（特にカオリン）を使用することが更に好ましく、平均粒子径５μｍ以上、且つアスペクト比が５０以上の無機顔料（特にカオリン）を使用することが特に好ましい。ガスバリア層に顔料を含有させた場合、酸素等のガスは顔料を迂回して通過する。このため、顔料を含有していない水溶性高分子からなるガスバリア層と比較して、良好な水蒸気バリア性及び高湿度雰囲気下における優れたガスバリア性を有する。(About pigment)
In the present invention, as pigments used for the gas barrier layer, kaolin, clay, engineered kaolin, layered clay, calcium carbonate, light calcium carbonate, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid And inorganic pigments such as silicate, colloidal silica, satin white and mica, and organic pigments such as solid, hollow or core-shell type. These can be used singly or in combination of two or more. Among these, it is preferable to use an inorganic pigment in terms of gas barrier properties.
It is more preferable to use an inorganic pigment (especially kaolin) having an average particle diameter of 3 μm or more and an aspect ratio of 10 or more, and use an inorganic pigment (especially kaolin) having an average particle diameter of 5 μm or more and an aspect ratio of 50 or more. Is particularly preferred. When the gas barrier layer contains a pigment, a gas such as oxygen bypasses the pigment and passes through. For this reason, compared with the gas barrier layer which consists of a water-soluble polymer which does not contain a pigment, it has the outstanding gas-barrier property in the favorable water vapor barrier property and high humidity atmosphere.
本発明において、ガスバリア層に含有する顔料と水溶性高分子の配合比率（乾燥重量）は顔料／水溶性高分子が１／１００〜１０００／１００であることが好ましい。顔料の比率が上記範囲外であると充分なガスバリア性が発揮しない。 In the present invention, the blending ratio (dry weight) of the pigment to the water-soluble polymer contained in the gas barrier layer is preferably 1/100 to 1000/100 of the pigment / water-soluble polymer. If the proportion of the pigment is outside the above range, sufficient gas barrier properties will not be exhibited.
（架橋剤について）
本発明において、ガスバリア層に多価金属塩等に代表される架橋剤を添加することが好ましい。架橋剤は水溶性高分子の水酸基どうしを架橋構造にて結合させるため、高湿度となった場合に結合が緩む(又は切れる)水酸基量が減少し、層全体の耐水性が向上するため、高湿度下での酸素バリア性の低下を抑制することができる。(About a crosslinking agent)
In the present invention, it is preferable to add a crosslinking agent represented by a polyvalent metal salt or the like to the gas barrier layer. The crosslinking agent combines the hydroxyl groups of the water-soluble polymer with a crosslinking structure, so that the amount of hydroxyl groups which loose (or break) the bond when high humidity is reduced and the water resistance of the whole layer is improved. It is possible to suppress the decrease in oxygen barrier properties under humidity.
本発明において、架橋剤の種類としては特に限定されるものではなく、水蒸気バリア層に含有されるバインダーの種類に合わせて、多価金属塩（銅、亜鉛、銀、鉄、カリウム、ナトリウム、ジルコニウム、アルミニウム、カルシウム、バリウム、マグネシウム、チタン等の多価金属と、炭酸イオン、硫酸イオン、硝酸イオン、燐酸イオン、珪酸イオン、窒素酸化物、ホウ素酸化物等のイオン性物質が結合した化合物）、アミン化合物、アミド化合物、アルデヒド化合物、ヒドロキシ酸等を適宜選択して使用することができる。架橋剤の配合部数においても塗工可能な塗料濃度や塗料粘度の範囲内であれば特に限定されることなく配合することができる。なお、水蒸気バリア性に優れた効果を発現するスチレン・ブタジエン系、スチレン・アクリル系等のスチレン系の水蒸気バリア性樹脂を用いた場合、架橋効果発現の観点から、多価金属塩を使用することが好ましく、カリウムミョウバンを使用することがより好ましい。
架橋剤の添加量は、ガスバリア層に使用される樹脂１００重量部に対して、１〜１０重量部であり、より好ましくは３〜５重量部である。１重量部より少ないと、十分な効果が得られず、１０重量部より多いと、塗工液の粘度が著しく増加するため、塗工困難になる。In the present invention, the kind of the crosslinking agent is not particularly limited, and a polyvalent metal salt (copper, zinc, silver, iron, potassium, sodium, zirconium) according to the kind of the binder contained in the water vapor barrier layer A compound in which a polyvalent metal such as aluminum, calcium, barium, magnesium, titanium, etc. and an ionic substance such as carbonate ion, sulfate ion, nitrate ion, phosphate ion, silicate ion, nitrogen oxide, boron oxide etc. An amine compound, an amide compound, an aldehyde compound, a hydroxy acid and the like can be appropriately selected and used. Also in the compounding | blending part number of a crosslinking agent, if it is in the range of the coating material density which can be coated, and a coating material viscosity, it can mix | blend, without being limited. In the case of using a styrene-butadiene-based or styrene-acrylic-based water-vapor barrier resin exhibiting an excellent effect on water-vapor barrier properties, polyvalent metal salts should be used from the viewpoint of the crosslinking effect. Is preferred, and potassium alum is more preferred.
The addition amount of the crosslinking agent is 1 to 10 parts by weight, more preferably 3 to 5 parts by weight with respect to 100 parts by weight of the resin used in the gas barrier layer. If the amount is less than 1 part by weight, a sufficient effect can not be obtained, and if the amount is more than 10 parts by weight, the viscosity of the coating liquid significantly increases, which makes coating difficult.
（添加剤）
本発明において、顔料を水溶性高分子中に配合する際に、顔料を水分散してスラリー化したものを添加し混合することが好ましい。
本発明において、ガスバリア層には、水溶性高分子、顔料の他、分散剤、増粘剤、保水剤、消泡剤、耐水化剤、染料、蛍光染料等の通常使用される各種助剤を使用することができる。(Additive)
In the present invention, when the pigment is blended in the water-soluble polymer, it is preferable to add and mix the pigment which is dispersed in water and made into a slurry.
In the present invention, the gas barrier layer may contain, in addition to water-soluble polymers and pigments, various commonly used auxiliary agents such as dispersants, thickeners, water retention agents, antifoaming agents, water resistance agents, dyes and fluorescent dyes. It can be used.
＜塗工について＞
本発明において、水蒸気バリア層、ガスバリア層の塗工方法については特に限定されるものではなく、公知の塗工装置を用いることができる。例えば、ブレードコーター、バーコーター、ロールコーター、エアナイフコーター、リバースロールコーター、カーテンコーター、スプレーコーター、サイズプレスコーター、ゲートロールコーター等が挙げられる。また、塗工層を乾燥させる手法としては、例えば、蒸気加熱ヒーター、ガスヒーター、赤外線ヒーター、電気ヒーター、熱風加熱ヒーター、マイクロウェーブ、シリンダードライヤー等の通常の方法が用いられる。<About coating>
In the present invention, the coating method of the water vapor barrier layer and the gas barrier layer is not particularly limited, and a known coating apparatus can be used. For example, a blade coater, a bar coater, a roll coater, an air knife coater, a reverse roll coater, a curtain coater, a spray coater, a size press coater, a gate roll coater and the like can be mentioned. Moreover, as a method of drying a coating layer, normal methods, such as a vapor heating heater, a gas heater, an infrared heater, an electric heater, a hot-air heater, a microwave, a cylinder drier, are used, for example.
本発明において、水蒸気バリア層の塗工量は、乾燥重量で４〜３０ｇ／ｍ2とすることが好ましく、より好ましくは６〜２５ｇ／ｍ2であり、更に好ましくは１０〜２０ｇ／ｍ2であることが好ましい。塗工量が３ｇ／ｍ2以下であると原紙を塗工液が完全に被覆することが困難となり、十分な水蒸気バリア性が得られない、ガスバリア層が紙基材に浸透するため、均一なガスバリア性が得られない問題がある。一方、３０ｇ／ｍ2以上であると、塗工時の乾燥負荷が大きくなり、操業面、コスト面の両方の観点より好ましくない。In the present invention, the coating amount of the water vapor barrier layer is preferably 4 to 30 g / m 2 on a dry weight basis, more preferably 6 to 25 g / m 2 , and still more preferably 10 to 20 g / m 2 . Is preferred. If the coating amount is 3 g / m 2 or less, it becomes difficult for the coating solution to completely cover the base paper, and sufficient water vapor barrier properties can not be obtained. There is a problem that gas barrier properties can not be obtained. On the other hand, when it is 30 g / m 2 or more, the drying load at the time of coating becomes large, which is not preferable from both the viewpoint of operation and cost.
本発明において、ガスバリア層の塗工量は、乾燥重量で０．２〜１０ｇ／ｍ2とすることが好ましい。塗工量が０．２／ｍ2未満であると均一なガスバリア層を形成することができないため、十分なガスバリア性が得られない問題がある。一方、１０ｇ／ｍ2以上であると、塗工時の乾燥負荷が大きくなり、操業面、コスト面の両方の観点より好ましくない。In the present invention, the coating amount of the gas barrier layer is preferably 0.2 to 10 g / m 2 on a dry weight basis. If the coating amount is less than 0.2 / m 2 , a uniform gas barrier layer can not be formed, so there is a problem that sufficient gas barrier properties can not be obtained. On the other hand, when it is 10 g / m 2 or more, the drying load at the time of coating becomes large, which is not preferable from both the viewpoint of operation and cost.
本発明において、紙基材上に水蒸気バリア層、ガスバリア層を設けた紙製バリア包装材料に、ポリエチレン、ポリプロピレン、ポリ酢酸ビニル重合体等のシーラント層を設けることができる。シーラント層の積層方法については特に制限されるものではないが、従来の溶融押し出しラミ法やフィルムを用いたドライラミ法、直接溶融コート法等公知の方法を用いることができる。 In the present invention, a sealant layer of polyethylene, polypropylene, polyvinyl acetate polymer or the like can be provided on a paper barrier packaging material provided with a water vapor barrier layer and a gas barrier layer on a paper substrate. The method for laminating the sealant layer is not particularly limited, and known methods such as a conventional melt extrusion lamination method, a dry lamination method using a film, a direct melt coating method and the like can be used.
以下に実施例を挙げて、本発明を具体的に説明するが、もちろんこれらの例に限定されるものではない。なお、特に断らない限り、例中の部及び％は、それぞれ重量部、重量％を示す。なお、塗工液及び得られた機能性紙について以下に示す様な評価法に基づいて試験を行った。試験結果を表１、表２に示す。 The present invention will be specifically described by way of the following examples, but of course the present invention is not limited to these examples. Unless otherwise stated, parts and% in the examples indicate parts by weight and% by weight, respectively. In addition, about the coating liquid and the obtained functional paper, the test was done based on the evaluation method as shown below. The test results are shown in Tables 1 and 2.
（評価方法）
（１）水蒸気透過度：温度４０±０．５℃、相対湿度９０±２％の条件下で、透湿度測定器(Ｄｒ．Ｌｙｓｓｙ社製Ｌ８０−４０００)を用いて測定した。
（２）酸素透過度：ＭＯＣＯＮ社製ＯＸ−ＴＲＡＮ２／２１を使用し、２３℃、０％ＲＨ条件及び２３℃、８５％ＲＨ条件にて測定した。
（３）接触角度：２３℃、５０％ＲＨ雰囲気下で、動的表面接触角測定装置（Ｆｉｂｒｏ社製ダイナミックアブソープションテスタ ＤＡＴ１１００）を用い、水滴を滴下後０．１秒後の表面接触角を測定した。
(４) 平均粒子径：試料スラリーを分散剤ヘキサメタリン酸ソーダ０．２重量％を添加した純水中で滴下混合して均一分散体とし、レーザー法粒度測定機（使用機器：マルバーン社製マスターサイザーＳ型）を使用して粒度測定する。
(５) アスペクト比：顔料の平面方向及び断面方向をＳＥＭ(走査型電子顕微鏡)を用いて撮影し、顔料配向面の直系と長さを測定して、［アスペクト比=顔料配向面の直径／厚さ］により算出した。(Evaluation method)
(1) Water vapor transmission rate: Measured using a moisture permeability measuring device (L80-4000 manufactured by Dr. Lyssy) under the conditions of a temperature of 40 ± 0.5 ° C. and a relative humidity of 90 ± 2%.
(2) Oxygen Permeability: Measured under conditions of 23 ° C., 0% RH and 23 ° C., 85% RH using OX-TRAN 2/21 manufactured by MOCON.
(3) Contact angle: in an atmosphere of 23 ° C. and 50% RH, using a dynamic surface contact angle measurement device (Dynamic Absorption Tester DAT1100 manufactured by Fibro), the surface contact angle after 0.1 seconds after dropping a water droplet Was measured.
(4) Average particle size: The sample slurry is mixed dropwise in pure water to which 0.2% by weight of dispersant hexametaphosphate sodium is added to obtain a uniform dispersion, and a laser method particle size measuring apparatus (equipment: Mastersizer manufactured by Malvern Co., Ltd. Particle size measurement using S type).
(5) Aspect ratio: The plane direction and cross-sectional direction of the pigment are photographed using a SEM (scanning electron microscope), and the straight line and the length of the pigment alignment plane are measured. [Aspect ratio = diameter of pigment alignment plane / Thickness] was calculated.
[実施例１］
(紙基材の作製)
カナダ式標準ろ水度(ＣＳＦ)５００ｍｌの広葉樹クラフトパルプ(ＬＢＫＰ)とＣＳＦ５３０ｍｌの針葉樹クラフトパルプ(ＮＢＫＰ)を８０／２０の重量比で配合して、原料パルプとした。原料パルプスラリーに、乾燥紙力増強剤として分子量２５０万のポリアクリルアミド(ＰＡＭ)を対絶乾パルプ重量あたり０．１％、サイズ剤としてアルキルケテンダイマー(ＡＫＤ)を対絶乾パルプ重量あたり０．３５％、湿潤紙力増強剤としてポリアミドエピクロロヒドリン(ＰＡＥＨ)系樹脂を対絶乾パルプ重量あたり０．１５％、更に歩留剤として分子量１０００万のポリアクリルアミド(ＰＡＭ)を対絶乾パルプ重量あたり０．０８％添加した後、デュオフォーマーＦＭ型抄紙機にて３００ｍ／ｍiｎの速度で抄紙し、坪量５９ｇ／ｍ2の紙を得た。次いで、得られた紙に固形分濃度２％に調製したポリビニルアルコール(クラレ社製ＰＶＡ１１７)をロッドメタリングサイズプレスで、両面に１．０ｇ／ｍ2塗工、乾燥し、坪両６０ｇ／ｍ2の原紙を得た。得られた原紙をチルドカレンダーを用いて、速度３００ｍiｎ／ｍ、線圧５０ｋｇｆ／ｃｍ、１パスにて平滑処理を行った。Example 1
(Preparation of paper base)
A Canadian standard freeness (CSF) 500 ml of hardwood kraft pulp (LBKP) and CSF 530 ml of softwood kraft pulp (NBKP) were blended at a weight ratio of 80/20 to make a raw material pulp. The raw material pulp slurry contains, as a dry strength agent, polyacrylamide (PAM) having a molecular weight of 2.5 million per 100% by weight of bone dry pulp, and 0.1% by weight of alkyl ketene dimer (AKD) as a sizing agent. 35%, polyamide epichlorohydrin (PAEH) based resin as wet paper strengthening agent to 0.15% per dry weight of dried pulp, and further, polyacrylamide (PAM) having a molecular weight of 10 million as a retention agent to dry dried pulp After the addition of 0.08% by weight, papermaking was carried out at a speed of 300 m / min with a Duoformer FM type paper machine to obtain a paper having a basis weight of 59 g / m 2 . Subsequently, polyvinyl alcohol (PVA 117 manufactured by Kuraray Co., Ltd.) prepared to a solid content concentration of 2% is applied to both sides of the obtained paper by 1.0 g / m 2 coating on both sides using a rod metalling size press, and dried. I got 2 base papers. The obtained base paper was smoothed using a chilled calender at a speed of 300 min / m, a linear pressure of 50 kgf / cm, and one pass.
(水蒸気バリア層用塗工液の調製)
大粒径エンジニアードカオリン（イメリス社製バリサーフＨＸ 粒子径９．０μｍ アスペクト比８０−１００）に分散剤としてポリアクリル酸ソーダを添加し（対無機顔料０．２部）、セリエミキサーで分散して固形分濃度５５%の大粒径カオリンスラリーを調製した。得られたカオリンスラリー中にスチレン・ブタジエン系ラテックス (日本ゼオン社製ＰＮＴ７８６８)を対顔料１００部(固形分)となるように配合し、固形分濃度５０％の塗工液Ａを得た。
(酸素バリア層用塗工液の調製)
ポリビニルアルコール(クラレ社製ＰＶＡ１１７)を固形分濃度１０％となるよう調製し、塗工液Ｂを得た。
(紙製バリア包装材料の作製)
得られた原紙上に塗工液Ａを塗工量（乾燥）１２ｇ/ｍ2となるよう塗工速度３００ｍ/ｍiｎでブレードコーターを用いて片面塗工、乾燥した後、その上に塗工液Ｂを塗工量（乾燥）２．０ｇ/ｍ２となるよう塗工速度３００ｍ/ｍiｎでロールコーターを用いて片面塗工し、紙製バリア包装材料を得た。(Preparation of Coating Solution for Water Vapor Barrier Layer)
Add sodium polyacrylate as a dispersant (to inorganic pigment 0.2 parts) as a dispersing agent to large particle size engineered kaolin (Varisurf HX manufactured by Imeris Co., Ltd. Particle diameter 9.0 μm, aspect ratio 80-100), and disperse with Serie mixer A large particle size kaolin slurry having a solid content concentration of 55% was prepared. In the obtained kaolin slurry, a styrene butadiene latex (PNT 7868 manufactured by Nippon Zeon Co., Ltd.) was blended so as to be 100 parts (solid content) of a pigment to obtain a coating liquid A having a solid content concentration of 50%.
(Preparation of coating liquid for oxygen barrier layer)
A polyvinyl alcohol (PVA 117 manufactured by Kuraray Co., Ltd.) was prepared to have a solid content concentration of 10%, to obtain a coating solution B.
(Preparation of paper barrier packaging material)
The coating solution A was coated on one side using a blade coater at a coating speed of 300 m / min so as to give a coating amount (dry) of 12 g / m 2 on the obtained base paper, and then dried. B was coated on one side using a roll coater at a coating speed of 300 m / min to a coating amount (dry) of 2.0 g / m 2 to obtain a paper barrier packaging material.
[実施例２］
酸素バリア層用塗工液において大粒径エンジニアードカオリン（イメリス社製バリサーフＨＸ）に分散剤としてポリアクリル酸ソーダを添加し（対無機顔料０．２部）、セリエミキサーで分散して固形分濃度５５％の大粒径カオリンスラリーを調製した。得られたカオリンスラリーと塗工液Ｂを固形分で顔料：塗工液Ｂ=１００：１００として固形分濃度が１０％となるよう混合した塗工液を使用した以外は実施例１と同様にして紙製バリア包装材料を得た。Example 2
In a coating solution for oxygen barrier layer, sodium polyacrylate as a dispersant is added to large particle size engineered kaolin (Varisurf HX manufactured by Imerisu Co., Ltd.) (0.2 parts of inorganic pigment), and dispersed by a serie mixer to obtain solid content A large particle size kaolin slurry having a concentration of 55% was prepared. The same procedure as in Example 1 was repeated except that the obtained kaolin slurry and the coating liquid B were mixed so that the solid content concentration would be 10% with the pigment: coating liquid B = 100: 100 as solid content. Paper barrier packaging material was obtained.
[実施例３］
酸素バリア層用塗工液においてカリウムミョウバン(関東化学社製硫酸カリウムアルミニウム・１２水和物)を濃度５％となるよう溶解し、得られたカリウムミョウバン水溶液を対ポリビニルアルコールに対して固形分で３部となるよう配合して固形分濃度が１０％の塗工液を使用した以外は実施例１と同様にして紙製バリア包装材料を得た。[Example 3]
Dissolve potassium alum (potassium aluminum sulfate 12 hydrate by Kanto Chemical Co., Ltd.) in the coating solution for oxygen barrier layer to a concentration of 5%, and use the obtained aqueous solution of potassium alum as a solid content against polyvinyl alcohol A paper barrier packaging material was obtained in the same manner as in Example 1 except that it was blended to be 3 parts and a coating liquid having a solid content concentration of 10% was used.
[実施例４］
酸素バリア層用塗工液において塗工液Ｂに実施例２にて調製したカオリンスラリーを固形分で顔料：塗工液Ｂ=１００：１００となるよう混合し、更に実施例３にて溶解したカリウムミョウバン水溶液を対ポリビニルアルコールに対して固形分で３部となるよう配合して固形分濃度が１０％の塗工液を使用した以外は実施例１と同様にして紙製バリア包装材料を得た。Example 4
In the coating liquid for oxygen barrier layer, the kaolin slurry prepared in Example 2 was mixed with the coating liquid B so that the pigment: coating liquid B = 100: 100 in solid content, and dissolved in Example 3 A paper barrier packaging material is obtained in the same manner as in Example 1 except that a potassium alum aqueous solution is mixed so that the solid content is 3 parts with respect to polyvinyl alcohol and a coating liquid having a solid content concentration of 10% is used. The
[実施例５］
水蒸気バリア層用塗工液において塗工液Ａの顔料中に重質炭酸カルシウムスラリー(ファイマテック社製、ＦＭＴ−７５、平均粒子径：１．６μｍ、アスペクト比：１)を顔料配合比で７５:２５となるように混合、撹拌した塗工液を用いた以外は実施例１と同様にして紙製バリア包装材料を得た。[Example 5]
Heavy calcium carbonate slurry (FMT-75, manufactured by Fimatech Co., Ltd., FMT-75, average particle size: 1.6 μm, aspect ratio: 1) in the pigment composition of the coating liquid A in the coating liquid for water vapor barrier layer A paper barrier packaging material was obtained in the same manner as in Example 1 except that the coating liquid was mixed and stirred so as to be 25:25.
[実施例６]
水蒸気バリア層用塗工液において実施例５にて得られた塗工液中に実施例３にて溶解したカリウムミョウバン水溶液を対顔料３部となるよう配合して、固形分濃度５０％の塗工液を用いた以外は実施例１と同様にして紙製バリア包装材料を得た。[Example 6]
The coating solution for water vapor barrier layer was mixed with the aqueous solution of potassium alum dissolved in Example 3 in the coating solution obtained in Example 5 so as to be 3 parts of a pigment, and the coating with a solid content concentration of 50% was applied. A paper barrier packaging material was obtained in the same manner as in Example 1 except that the working fluid was used.
[実施例７]
酸素バリア層用塗工液において実施例４にて得られた塗工液を用いて、水蒸気バリア層用塗工液を実施例５にて得られた塗工液を用いた以外は実施例１と同様にして紙製バリア包装材料を得た。[Example 7]
Example 1 except using the coating liquid obtained in Example 5 using the coating liquid obtained in Example 4 in the coating liquid for oxygen barrier layer A paper barrier packaging material was obtained in the same manner as in.
[実施例８]
酸素バリア層用塗工液において実施例４にて得られた塗工液を用いて、水蒸気バリア層用塗工液を実施例６にて得られた塗工液を用いた以外は実施例１と同様にして紙製バリア包装材料を得た。[Example 8]
Example 1 except using the coating liquid obtained in Example 6 using the coating liquid obtained in Example 4 in the coating liquid for oxygen barrier layer A paper barrier packaging material was obtained in the same manner as in.
[実施例９]
酸素バリア層用塗工液において実施例２にて得られた塗工液中の大粒径エンジニアードカオリンからマイカ（松尾産業株式会社製Ｂ−８２ 粒子径：１８０μｍ）に変更した以外は実施例２と同様にして紙製バリア包装材料を得た。[Example 9]
Example except that the large particle size engineered kaolin in the coating liquid obtained in Example 2 was changed to mica (B-82 particle size: 180 μm manufactured by Matsuo Sangyo Co., Ltd.) in the coating liquid for oxygen barrier layer A paper barrier packaging material was obtained in the same manner as 2).
[実施例１０]
酸素バリア層用塗工液において実施例１にて得られた塗工液中の大粒径エンジニアードカオリンからモンモリロナイト（東新化成株式会社製ニッカナイト Ａ−３６粒子径：４００μｍ）に変更した以外は実施例１と同様にして紙製バリア包装材料を得た。[Example 10]
Except that the large particle size engineered kaoline in the coating liquid obtained in Example 1 was changed to montmorillonite (Nikkanite A-36 particle diameter: 400 μm manufactured by Toshin Kasei Co., Ltd.) in the coating liquid for oxygen barrier layer in the coating liquid for oxygen barrier layer A paper barrier packaging material was obtained in the same manner as in Example 1.
[実施例１１]
水蒸気バリア層用塗工液において実施例１にて得られた塗工液中の大粒径エンジニアードカオリンからマイカ（松尾産業株式会社製Ｂ−８２ 粒子径：１８０μｍ）に変更し、顔料分散濃度を２０％、塗工液濃度を３０に変更した以外は実施例１と同様にして紙製バリア包装材料を得た。[Example 11]
In the coating solution for water vapor barrier layer, the large particle size engineered kaolin in the coating solution obtained in Example 1 is changed to mica (B-82 particle size: 180 μm manufactured by Matsuo Sangyo Co., Ltd.), and the pigment dispersion concentration is A paper barrier packaging material was obtained in the same manner as in Example 1 except that the concentration of the coating liquid was changed to 20% and the concentration of the coating liquid was changed to 30.
[実施例１２]
水蒸気バリア層用塗工液において実施例１にて得られた塗工液中の大粒径エンジニアードカオリンからモンモリロナイト（東新化成株式会社製ニッカナイト Ａ−３６粒子径：４００μｍ）に変更し、顔料分散濃度を２０％、塗工液濃度を３０％に変更し、塗工量を９ｇ／ｍ2に変更した以外は実施例１と同様にして紙製バリア包装材料を得た。[Example 12]
In the coating solution for a water vapor barrier layer, the large particle size engineered kaolin in the coating solution obtained in Example 1 is changed to montmorillonite (Nikkanite A-36 particle size: 400 μm manufactured by Toshin Kasei Co., Ltd.), A paper barrier packaging material was obtained in the same manner as in Example 1 except that the pigment dispersion concentration was changed to 20%, the coating liquid concentration to 30%, and the coating amount to 9 g / m 2 .
[実施例１３]
水蒸気バリア層用塗工液において実施例１のスチレン・ブタジエン系ラテックスからアクリルスチレン系共重合体エマルジョン（サイデン化学社製サイビノールＸ−５１１−３７４Ｅ）に変更した以外は実施例１と同様にして紙製バリア包装材料を得た。[Example 13]
A paper was prepared in the same manner as in Example 1 except that the styrene butadiene latex of Example 1 was changed to an acrylic styrene copolymer emulsion (Cybinol X-511-374E manufactured by Siden Chemical Co., Ltd.) in the coating liquid for water vapor barrier layer. Obtained barrier packaging material.
[実施例１４]
水蒸気バリア層用塗工液においてスチレン・ブタジエン系ラテックス（旭化成ケミカルズ社製Ｌ７３６０）に変更した以外は実施例１と同様にして紙製バリア包装材料を得た。Example 14
A paper barrier packaging material was obtained in the same manner as in Example 1 except that the coating solution for a water vapor barrier layer was changed to a styrene butadiene latex (L7360 manufactured by Asahi Kasei Chemicals Corporation).
[実施例１５］
水蒸気バリア層用塗工液において、塗工液中に用いる顔料を大粒径エンジニアードカオリン（イメリス社製バリサーフＨＸ）から大粒径エンジニアードカオリン（イメリス社製Ｃａｐｉｍ ＣＣ、粒子径：８．０μｍ、アスペクト比：１０〜１５）に変更した以外は実施例１と同様にして紙製バリア包装材料を得た。[Example 15]
In the coating solution for water vapor barrier layer, the pigment used in the coating solution is made from large particle size engineered kaolin (Varisurf HX manufactured by Imeris Co., Ltd.) large particle size engineered Kaoline (Capim CC manufactured by Imeris Co., Ltd., particle size: 8.0 μm) The paper barrier packaging material was obtained in the same manner as in Example 1 except that the aspect ratio was changed to 10 to 15).
[実施例１６］
水蒸気バリア層用塗工液において、塗工液中に用いる顔料を大粒径エンジニアードカオリン（イメリス社製バリサーフＨＸ）から微粒カオリン（ＫａＭｉｎ社製、Ｈｙｄｒａｇｌｏｓｓ、平均粒子径：０．３μｍ、アスペクト比：１０〜１５）に変更した以外は実施例１と同様にして紙製バリア包装材料を得た。[Example 16]
In the coating solution for water vapor barrier layer, the pigment used in the coating solution is made from large particle size engineered kaolin (Varisurf HX manufactured by Imeris) to fine particle kaolin (manufactured by KaMin, Hydragloss, average particle size: 0.3 μm, aspect ratio) A paper barrier packaging material was obtained in the same manner as in Example 1 except that it was changed to 10:15).
[実施例１７］
水蒸気バリア層用塗工液において、塗工液中に用いる顔料を大粒径エンジニアードカオリン（イメリス社製バリサーフＨＸ）から２級カオリン(イメリス社製ＫＣＳ、平均粒子径：３．６μｍ、アスペクト比：１０〜１５)に変更した以外は実施例１と同様にして紙製バリア包装材料を得た。[Example 17]
In the coating solution for water vapor barrier layer, the pigment used in the coating solution is made from large particle size engineered kaolin (Varisurf HX manufactured by Imeris Co., Ltd.) to second grade kaolin (KCS manufactured by Imeris Co., Ltd., average particle size: 3.6 μm, aspect ratio A paper barrier packaging material was obtained in the same manner as in Example 1 except that it was changed to 10:15).
[実施例１８］
水蒸気バリア層用塗工液において、塗工液中に用いるラテックスをスチレン・ブタジエン系ラテックス（日本ゼオン社製ＰＮＴ７８８９）に変更した以外は実施例１と同様にして紙製バリア包装材料を得た。[Example 18]
A paper barrier packaging material was obtained in the same manner as in Example 1 except that the latex used in the coating liquid in the coating liquid for a water vapor barrier layer was changed to a styrene butadiene latex (PNT7889 manufactured by Nippon Zeon Co., Ltd.).
[実施例１９］
水蒸気バリア層用塗工液において、塗工液中に用いるラテックスをスチレン・ブタジエン系ラテックス（旭化成ケミカルズ社製Ｌ７３６０）に変更した以外は実施例１と同様にして紙製バリア包装材料を得た。[Example 19]
A paper barrier packaging material was obtained in the same manner as in Example 1 except that the latex used in the coating liquid in the coating liquid for a water vapor barrier layer was changed to a styrene butadiene latex (L7360 manufactured by Asahi Kasei Chemicals Corporation).
[実施例２０］
水蒸気バリア層用塗工液において、塗工液中に用いるラテックスをアクリル系共重合体ラテックス（旭化成ケミカルズ社製Ｅ３１６）に変更した以外は実施例１と同様にして紙製バリア包装材料を得た。[Example 20]
A paper barrier packaging material was obtained in the same manner as in Example 1 except that the latex used in the coating liquid in the coating liquid for a water vapor barrier layer was changed to an acrylic copolymer latex (E316 manufactured by Asahi Kasei Chemicals Corporation). .
[実施例２１］
水蒸気バリア層用塗工液において、塗工液中に用いるラテックスをアクリル共重合体水系エマルジョン（サイデン化学社製ＥＫ-６１）に変更した以外は実施例１と同様にして紙製バリア包装材料を得た。[Example 21]
A paper barrier packaging material was prepared in the same manner as in Example 1 except that the latex used in the coating liquid in the coating liquid for a water vapor barrier layer was changed to an acrylic copolymer aqueous emulsion (EK-61 manufactured by Siden Chemical Co., Ltd.). Obtained.
[実施例２２］
塗工液Ａの塗工量を、乾燥重量で１２ｇ／ｍ2から６ｇ／ｍ2に変更した以外は実施例１と同様にして紙製バリア包装材料を得た。Example 22
The coating amount of the coating liquid A, except for changing from 12 g / m 2 to 6 g / m 2 in dry weight in the same manner as in Example 1 to obtain a paper barrier packaging materials.
[実施例２３］
塗工液Ａの塗工量にを、乾燥重量で１２ｇ／ｍ2から１５ｇ／ｍ2に変更した以外は実施例１と同様にして紙製バリア包装材料を得た。[Example 23]
To coverage of the coating liquid A, except for changing from 12 g / m 2 to 15 g / m 2 in dry weight in the same manner as in Example 1 to obtain a paper barrier packaging materials.
[実施例２４］
塗工液Ｂの塗工量を、乾燥重量で２ｇ／ｍ2から１ｇ／ｍ2に変更した以外は実施例１と同様にして紙製バリア包装材料を得た。[Example 24]
The coating amount of the coating liquid B, and dry weight of 2 g / m 2 was changed to 1 g / m 2 in the same manner as in Example 1 to obtain a paper barrier packaging materials.
[実施例２５］
塗工液Ｂの塗工量を、乾燥重量で２ｇ／ｍ2から４ｇ／ｍ2に変更した以外は実施例１と同様にして紙製バリア包装材料を得た。[Example 25]
The coating amount of the coating liquid B, and dry weight of 2 g / m 2 was changed to 4g / m 2 in the same manner as in Example 1 to obtain a paper barrier packaging materials.
[実施例２６］
水蒸気バリア層用塗工液の調製において、スチレン・ブタジエン系ラテックス(日本ゼオン社製ＰＮＴ７８６８)の配合量を対顔料１００部から５０部(固形分)に変更した以外は実施例１と同様にして紙製バリア包装材料を得た。[Example 26]
The same procedure as in Example 1 was repeated except that the blending amount of the styrene butadiene latex (PNT 7868 manufactured by Nippon Zeon Co., Ltd.) was changed from 100 parts to 50 parts of the pigment (solid content) in the preparation of the coating liquid for water vapor barrier layer A paper barrier packaging material was obtained.
[実施例２７］
水蒸気バリア層用塗工液の調製において、スチレン・ブタジエン系ラテックス(日本ゼオン社製ＰＮＴ７８６８)の配合量を対顔料１００部から１５０部(固形分)に変更した以外は実施例１と同様にして紙製バリア包装材料を得た。[Example 27]
The same procedure as in Example 1 was repeated except that the blending amount of the styrene butadiene latex (PNT 7868 manufactured by Nippon Zeon Co., Ltd.) was changed from 100 parts to 150 parts of pigment (solid content) in the preparation of the coating liquid for water vapor barrier layer A paper barrier packaging material was obtained.
[実施例２８］
酸素バリア層用塗工液の調製において、カオリンスラリーの配合量を固形分で顔料：塗工液Ｂ＝１００：１００から１５０：１００となるよう変更した以外は実施例２と同様にして紙製バリア包装材料を得た。[Example 28]
In the preparation of the coating liquid for oxygen barrier layer, paper is prepared in the same manner as in Example 2 except that the blending amount of kaolin slurry is changed so that the solid content is pigment: coating liquid B = 100: 100 to 150: 100. Obtained barrier packaging material.
[実施例２９］
酸素バリア層用塗工液の調製において、カオリンスラリーの配合量を固形分で顔料：塗工液Ｂ＝１００：１００から５０：１００となるよう変更した以外は実施例２と同様にして紙製バリア包装材料を得た。[Example 29]
In the preparation of the coating liquid for oxygen barrier layer, paper is prepared in the same manner as in Example 2 except that the blending amount of kaolin slurry is changed so that the solid content is pigment: coating liquid B = 100: 100 to 50: 100. Obtained barrier packaging material.
[比較例１］
紙基材にガスバリア層、水蒸気バリア層をこの順に設けた以外は実施例１と同様にして紙製バリア包装材料を得た。Comparative Example 1
A paper barrier packaging material was obtained in the same manner as in Example 1 except that a gas barrier layer and a water vapor barrier layer were provided in this order on the paper substrate.
[比較例２］
水蒸気バリア層を設けなかった以外は実施例１と同様にして紙製バリア包装材料を得た。Comparative Example 2
A paper barrier packaging material was obtained in the same manner as in Example 1 except that the water vapor barrier layer was not provided.
[比較例３］
ガスバリア層を設けなかった以外は実施例１と同様にして紙製バリア包装材料を得た。Comparative Example 3
A paper barrier packaging material was obtained in the same manner as in Example 1 except that the gas barrier layer was not provided.
＜考察＞
この実施例、比較例の試験データから次のような特質を挙げることができる。
（１）実施例１、比較例１、２、３のデータから、紙基材上に水蒸気バリア層を形成し、更にその上にガスバリア層を形成した実施例１は、水蒸気透過度、酸素透過度も低い。これに対して、ガスバリア層を設けただけの比較例２は、酸素透過度と水蒸気透過度が非常に大きく、どちらのバリア性機能も発揮していない、水蒸気バリア層のみを設けた比較例３とガスバリア層の上に水蒸気バリア層を設けた比較例１では、水蒸気バリア性は実施例１と同程度の機能を発揮しているが、ガスバリア性は全く観察されない。これは、紙基材を透過した水分がガスバリア層を劣化させた結果を示している。したがって、紙基材の上に水蒸気バリア層を設け更にその上にガスバリア層を形成した本発明の有用性が明確に示された結果を示している。
（２）水蒸気バリア層の塗工料に架橋剤であるカリウムミョウバンを添加した実施例６、８では、実施例１よりも水蒸気バリア性が向上している。
（３）水蒸気バリア層の塗工料に、扁平度の大きな大粒径のカオリンと重炭酸カルシウム微粒子と大小の顔料を併用した実施例５、７は、実施例１よりも水蒸気バリア性が向上している。
（４）アスペクト比が８０以上の大粒径顔料である、カオリン、マイカ（実施例１１）、モンモリロナイト（実施例１２）が有効であることが確認できた、特に、大粒径でアスペクト比８０以上のカオリンが他の顔料よりも優れた水蒸気バリア性を示した。
（５）ガスバリア層に大粒径カオリン、マイカ、モンモリロナイト（以上大粒径顔料）、カルシウムミョウバン（架橋剤）を単独あるいは併用して添加した、実施例２、３、４、７、８、９、１０の結果から、高湿度環境下において、ガスバリア性の性能が低下が小さく抑えることができる。
（６）水蒸気バリア層の水滴の接触角が、実施例１等の７５度よりも大きな９０度（実施例１３）、８０度（実施例１４、２１、２２）の場合は、高湿度環境下において、ガスバリア性の性能が低下が若干大きくなっており、水滴の接触角が小さい方が湿度変化による性能低下を防止できる。
（７）実施例１、１５、１６、１７の結果から、水蒸気針性能は水蒸気バリア層に添加する顔料の粒径に依存する傾向が認められる。そして、高湿度環境下におけるガスバリア性能も同様に粒径依存性が認められた。
（８）実施例１、１４、１８、１９、２０、２１の結果から、水蒸気バリア層を形成する塗工料に用いるバインダー樹脂として、スチレン・ブタジエン系、アクリル系今日重合体が有用であることが確認できた。
（９）水蒸気バリア層の塗工量（乾燥重量）は、６〜１５ｇ／ｍ2、ガスバリア層の塗工量（乾燥重量）は１〜４ｇ／ｍ2の範囲では十分な水蒸気バリア性とガスバリア性を発揮することが確認できた。<Discussion>
The following characteristics can be mentioned from the test data of this example and comparative example.
(1) From the data of Example 1, Comparative Examples 1, 2 and 3, Example 1 in which a water vapor barrier layer was formed on a paper substrate and a gas barrier layer was further formed thereon, the water vapor permeability, oxygen permeation The degree is also low. On the other hand, Comparative Example 2 in which only the gas barrier layer is provided is Comparative Example 3 in which only the water vapor barrier layer is provided, in which the oxygen permeability and the water vapor permeability are very large and neither barrier function is exhibited. In Comparative Example 1 in which the water vapor barrier layer is provided on the gas barrier layer, the water vapor barrier property exhibits the same function as in Example 1, but the gas barrier property is not observed at all. This shows the result that the moisture which permeated the paper base material deteriorated the gas barrier layer. Accordingly, the results clearly show the usefulness of the present invention in which the water vapor barrier layer is provided on the paper substrate and the gas barrier layer is formed thereon.
(2) In Examples 6 and 8 in which potassium alum, which is a crosslinking agent, is added to the coating material for the water vapor barrier layer, the water vapor barrier properties are improved more than in Example 1.
(3) The water vapor barrier properties of Examples 5 and 7 in which large particle size kaolin with large flatness, calcium bicarbonate fine particles, and large and small pigments are used in combination in the coating material for the water vapor barrier layer have improved water vapor barrier properties over Example 1. ing.
(4) It was confirmed that kaolin, mica (Example 11) and montmorillonite (Example 12), which are large particle size pigments having an aspect ratio of 80 or more, were effective. The above kaolin showed superior water vapor barrier properties to other pigments.
(5) Examples 2, 3, 4, 7, 8 and 9 in which large particle size kaolin, mica, montmorillonite (more than large particle size pigment) and calcium alum (crosslinking agent) were added alone or in combination to the gas barrier layer. From the results of 10, in the high humidity environment, the deterioration of the gas barrier performance can be suppressed to a small level.
(6) When the contact angle of water droplets in the water vapor barrier layer is 90 degrees (Example 13) or 80 degrees (Examples 14, 21 and 22) larger than 75 degrees of Example 1 etc., under high humidity environment In the above, the decrease in the performance of the gas barrier property is a little larger, and the smaller the contact angle of the water droplet, the more the deterioration of the performance due to the humidity change can be prevented.
(7) From the results of Examples 1, 15, 16 and 17, the steam needle performance tends to depend on the particle size of the pigment added to the steam barrier layer. And, the gas barrier performance in a high humidity environment was also found to be similarly dependent on the particle size.
(8) From the results of Examples 1, 14, 18, 19, 20, 21 that styrene-butadiene-based and acrylic-based polymers are useful as a binder resin used for a coating material for forming a water vapor barrier layer It could be confirmed.
(9) The coating amount (dry weight) of the water vapor barrier layer is 6 to 15 g / m 2 , and the coating amount (dry weight) of the gas barrier layer is 1 to 4 g / m 2. It has been confirmed that it exerts its character.
Claims (9)
該複数の塗工層が紙基材上に形成された水蒸気バリア層、該水蒸気バリア層上に形成されたガスバリア層を含んでおり、
これらの塗工層には、顔料を含み、バインダー樹脂として水溶性高分子あるいは水中懸濁性高分子が用いられており、
水蒸気バリア層には、前記顔料として、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％含有されており
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ことを特徴とする紙製バリア包装材料。 A paper barrier packaging material having a plurality of coating layers provided on a paper substrate,
The plurality of coating layers include a water vapor barrier layer formed on a paper substrate, and a gas barrier layer formed on the water vapor barrier layer,
These coating layers comprises a pigment, a water-soluble polymer or water suspension of high molecules are used as a binder resin,
The water vapor barrier layer contains, as the pigment, 50 to 100% by weight of kaolin having an average particle diameter of 5 μm or more and an aspect ratio of 10 or more with respect to all the pigments.
The binder resin of the gas barrier layer is polyvinyl alcohol resin, and the paper barrier packaging material characterized by the above-mentioned.
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| PCT/JP2012/079176 WO2013069788A1 (en) | 2011-11-10 | 2012-11-09 | Barrier paper packaging material |
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| US11280049B2 (en) | 2018-10-26 | 2022-03-22 | Oji Holdings Corporation | Gas barrier laminate and method for producing same |
| EP3733406B1 (en) * | 2017-10-04 | 2022-04-06 | Nippon Paper Industries Co., Ltd | Barrier material |
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| CN116219793A (en) * | 2022-12-26 | 2023-06-06 | 上海东冠纸业有限公司 | Paper-based packaging material and preparation method thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000177244A (en) * | 1998-12-11 | 2000-06-27 | Fuji Photo Film Co Ltd | Thermal recording material |
| JP2000303386A (en) * | 1999-04-19 | 2000-10-31 | Oji Paper Co Ltd | Moistureproof laminate with barrier properties |
| JP2002326321A (en) * | 2001-04-27 | 2002-11-12 | Toppan Printing Co Ltd | Gas barrier packaging material |
| JP2004017993A (en) * | 2002-06-13 | 2004-01-22 | Dainippon Printing Co Ltd | Paper container |
| JP2005162213A (en) * | 2003-11-28 | 2005-06-23 | Daio Paper Corp | Wrapping paper |
| JP2008087784A (en) * | 2006-09-29 | 2008-04-17 | Dainippon Printing Co Ltd | Packaging material |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0764739B1 (en) * | 1995-09-22 | 2001-01-24 | Oji Paper Co., Ltd. | Moisture-proof paper sheet |
| SE516817C2 (en) * | 1999-09-07 | 2002-03-05 | Tetra Laval Holdings & Finance | Process for producing a laminated packaging material, packaging material made according to this procedure, and packaging made from this packaging material |
| US20030027708A1 (en) * | 2001-07-18 | 2003-02-06 | Michael Ginn | Novel clay and products |
| JP2003094574A (en) | 2001-09-27 | 2003-04-03 | Kuraray Co Ltd | Paper laminate having barrier property and its production method |
| AU2002335033A1 (en) * | 2002-10-15 | 2004-05-04 | Dow Global Technologies Inc. | Method of producing a multilayer coated substrate having improved barrier properties |
| JP2009184138A (en) | 2008-02-04 | 2009-08-20 | Oji Paper Co Ltd | Gas-barrier laminate |
-
2012
- 2012-11-09 JP JP2013505656A patent/JP5331265B1/en active Active
- 2012-11-09 WO PCT/JP2012/079176 patent/WO2013069788A1/en active Application Filing
- 2012-11-09 EP EP12847115.8A patent/EP2777934B1/en active Active
- 2012-11-09 CN CN201280054858.5A patent/CN104080607B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000177244A (en) * | 1998-12-11 | 2000-06-27 | Fuji Photo Film Co Ltd | Thermal recording material |
| JP2000303386A (en) * | 1999-04-19 | 2000-10-31 | Oji Paper Co Ltd | Moistureproof laminate with barrier properties |
| JP2002326321A (en) * | 2001-04-27 | 2002-11-12 | Toppan Printing Co Ltd | Gas barrier packaging material |
| JP2004017993A (en) * | 2002-06-13 | 2004-01-22 | Dainippon Printing Co Ltd | Paper container |
| JP2005162213A (en) * | 2003-11-28 | 2005-06-23 | Daio Paper Corp | Wrapping paper |
| JP2008087784A (en) * | 2006-09-29 | 2008-04-17 | Dainippon Printing Co Ltd | Packaging material |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10882676B2 (en) | 2016-09-30 | 2021-01-05 | Nippon Paper Industries Co., Ltd. | Paper barrier material |
| EP3733406B1 (en) * | 2017-10-04 | 2022-04-06 | Nippon Paper Industries Co., Ltd | Barrier material |
| US11504952B2 (en) | 2017-10-04 | 2022-11-22 | Nippon Paper Industries Co., Ltd. | Barrier material |
| US11280049B2 (en) | 2018-10-26 | 2022-03-22 | Oji Holdings Corporation | Gas barrier laminate and method for producing same |
| US11905662B2 (en) | 2019-03-18 | 2024-02-20 | Nippon Paper Industries Co., Ltd. | Paper barrier material |
| WO2023132021A1 (en) | 2022-01-06 | 2023-07-13 | 大日本印刷株式会社 | Oxygen-absorbing coated multilayer body |
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