JP2022186782A - Water-resistant paper and liquid container - Google Patents
Water-resistant paper and liquid container Download PDFInfo
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- JP2022186782A JP2022186782A JP2022163971A JP2022163971A JP2022186782A JP 2022186782 A JP2022186782 A JP 2022186782A JP 2022163971 A JP2022163971 A JP 2022163971A JP 2022163971 A JP2022163971 A JP 2022163971A JP 2022186782 A JP2022186782 A JP 2022186782A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 415
- 239000007788 liquid Substances 0.000 title claims description 314
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 claims abstract description 67
- 239000011146 organic particle Substances 0.000 claims abstract description 66
- 239000000758 substrate Substances 0.000 claims abstract description 30
- 238000002844 melting Methods 0.000 claims abstract description 14
- 230000008018 melting Effects 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims description 393
- 238000000576 coating method Methods 0.000 claims description 393
- 239000002245 particle Substances 0.000 claims description 41
- 239000004698 Polyethylene Substances 0.000 claims description 21
- 238000007789 sealing Methods 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 18
- 239000011347 resin Substances 0.000 claims description 18
- -1 polypropylene Polymers 0.000 claims description 16
- 239000011436 cob Substances 0.000 claims description 10
- 230000035699 permeability Effects 0.000 claims description 10
- 229920000098 polyolefin Polymers 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 229920005653 propylene-ethylene copolymer Polymers 0.000 claims description 3
- 239000000123 paper Substances 0.000 description 283
- 239000010410 layer Substances 0.000 description 242
- 238000002360 preparation method Methods 0.000 description 88
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- 239000007787 solid Substances 0.000 description 68
- 230000000052 comparative effect Effects 0.000 description 57
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- 239000002585 base Substances 0.000 description 22
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- 238000000034 method Methods 0.000 description 14
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 8
- 229920001131 Pulp (paper) Polymers 0.000 description 7
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- PZWQOGNTADJZGH-SNAWJCMRSA-N (2e)-2-methylpenta-2,4-dienoic acid Chemical compound OC(=O)C(/C)=C/C=C PZWQOGNTADJZGH-SNAWJCMRSA-N 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
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- 150000001768 cations Chemical class 0.000 description 4
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- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
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- 235000013305 food Nutrition 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
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- 229910021645 metal ion Inorganic materials 0.000 description 3
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- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 235000013361 beverage Nutrition 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- 239000013054 paper strength agent Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000013055 pulp slurry Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920003182 Surlyn® Polymers 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229920002522 Wood fibre Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
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- 239000011575 calcium Substances 0.000 description 1
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- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- PDEDQSAFHNADLV-UHFFFAOYSA-M potassium;disodium;dinitrate;nitrite Chemical compound [Na+].[Na+].[K+].[O-]N=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PDEDQSAFHNADLV-UHFFFAOYSA-M 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
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- 235000009566 rice Nutrition 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
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- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging
Abstract
Description
本発明は、耐水性紙、およびこれを用いてなる液体容器に関する。 The present invention relates to water-resistant paper and liquid containers using the same.
飲料、食品等の各種容器として、従来プラスチック製品が使用されてきたが、環境負荷低減を目的として、紙製品への転換が望まれている。
従来、基紙の片面にポリエチレンフィルムをラミネートしたポリエチレンラミネート紙が、飲料、食品等の各種容器に使用されてきたが、再生時にポリエチレンフィルムの除去が困難であり、再生利用性に劣るという問題があった。
このような問題に対応するために、抄紙工程での性能の付与や、塗工による性能の付与により、耐水性等を付与することが行われてきた。
特許文献１には、耐水性、ヒートシール性、トップカール適性、グラビア印刷適性等の加工適性がポリエチレンラミネート紙と同等であり、かつ資源の有効利用のための再生性に優れたカップ原紙、カップ蓋原紙、紙皿原紙等の紙器原紙を提供することを目的として、基紙の少なくとも片面に目止め用の下塗り層、耐水耐油層からなる上塗り層を設けた紙器原紙において、下塗り層が顔料／バインダー樹脂層からなり塗工量が片面当り４～１５ｇ／ｍ２、上塗り層の耐水耐油層の樹脂塗工量が片面当り２ｇ／ｍ２以上であり、かつ下記Ａ～Ｄの要件を満足することを特徴とする紙器原紙が記載されている。
Ａ．基紙のコッブの吸水度が５０ｇ／ｍ２以下、平滑度が１０秒以上である。
Ｂ．下塗り層の使用顔料がアスペクト比５～３０、平均粒子径が０．５～３０μｍである。
Ｃ．下塗り層の配合比率が顔料１００質量部に対してバインダー樹脂が１０～１００質量部である。
Ｄ．上塗り層に使用する耐水耐油樹脂がゲル分率７０％以上を有し、塗工層の臨界表面張力が２５ｄｙｎ／ｃｍ以上である水分散系樹脂を使用する。
Conventionally, plastic products have been used as various containers for beverages, food, etc. However, in order to reduce the burden on the environment, it is desired to switch to paper products.
Conventionally, polyethylene-laminated paper, in which a polyethylene film is laminated on one side of the base paper, has been used for various containers such as beverages and foods. there were.
In order to deal with such problems, water resistance and the like have been imparted by imparting performance in the papermaking process and imparting performance by coating.
Patent Document 1 discloses a cup base paper and a cup that have processing aptitudes such as water resistance, heat sealability, top curl aptitude, and gravure printing aptitude equivalent to polyethylene-laminated paper, and that are highly recyclable for effective use of resources. For the purpose of providing base paper for paper containers such as base paper for lids and base paper for paper plates, base paper for paper containers is provided with an undercoat layer for filling and a topcoat layer consisting of a waterproof and oil-resistant layer on at least one side of the base paper. Consisting of a binder resin layer, the coating amount per side is 4 to 15 g/m 2 , the resin coating amount of the water- and oil-resistant layer of the topcoat layer is 2 g/m 2 or more per side, and the requirements A to D below are satisfied. A paper container base paper characterized by:
A. Cobb of the base paper has a water absorbency of 50 g/m 2 or less and a smoothness of 10 seconds or more.
B. The pigment used in the undercoat layer has an aspect ratio of 5 to 30 and an average particle size of 0.5 to 30 μm.
C. The mixing ratio of the undercoat layer is 10 to 100 parts by weight of the binder resin per 100 parts by weight of the pigment.
D. A water- and oil-resistant resin used in the overcoat layer has a gel fraction of 70% or more, and a water-dispersible resin having a critical surface tension of 25 dyn/cm or more in the coating layer is used.
また、特許文献２には、プラスチックの使用量を低減することができる包装用紙を提供することを目的として、紙基材の少なくとも一方の面に少なくとも１層のヒートシール層を有する包装用紙であって、前記ヒートシール層がアイオノマーを含み、前記ヒートシール層の乾燥塗工量が全層で２～１０ｇ／ｍ２であり、前記ヒートシール層が少なくとも一方の面に２層以上形成されていることを特徴とする包装用紙が記載されている。 Further, Patent Document 2 discloses a packaging paper having at least one heat-seal layer on at least one surface of a paper substrate for the purpose of providing a packaging paper that can reduce the amount of plastic used. The heat seal layer contains an ionomer, the dry coating amount of the heat seal layer is 2 to 10 g/m 2 in all layers, and the heat seal layer is formed in two or more layers on at least one surface. A packaging paper characterized by
耐水性紙は、連続的に製造する場合、ロールに巻き取りながら製造されるが、その際に、巻き取られた耐水性紙の塗工面が、耐水性紙の裏面に貼り付き、剥がれが生じる（ブロッキングする）という問題があった。このような問題について、特許文献１および２では改善の余地がある。
本発明は、耐水性に優れるとともに、耐ブロッキング性およびヒートシール性に優れた耐水性紙を提供することを目的とする。
In the case of continuous production, water-resistant paper is produced while being wound on a roll, but at that time, the coated surface of the wound water-resistant paper sticks to the back surface of the water-resistant paper, causing peeling. (blocking) was a problem. Regarding such problems, there is room for improvement in Patent Documents 1 and 2.
An object of the present invention is to provide a water-resistant paper excellent in water resistance, blocking resistance and heat-sealing property.
本発明者は、耐水性層にエチレン－メタクリル酸共重合体を配合するとともに、さらに特定の融点または軟化点を有する有機粒子を、特定量配合することにより、耐水性に優れるとともに、耐ブロッキング性およびヒートシール性に優れる耐水性紙が得られることを見出した。本発明は以下の＜１＞～＜１６＞に関する。
＜１＞ 紙基材の少なくとも一方の面の最上層に耐水性層を有する耐水性紙であり、該耐水性層が、エチレン－メタクリル酸共重合体、および有機粒子を含有し、該有機粒子の融点または軟化点が１００℃以上であり、耐水性層中の有機粒子の含有量が４０質量％以下である、耐水性紙。
＜２＞ 有機粒子の平均粒径が０．０１μｍ以上５０μｍ以下である、＜１＞に記載の耐水性紙。
＜３＞ 有機粒子がポリオレフィン粒子である、＜１＞または＜２＞に記載の耐水性紙。
＜４＞ 有機粒子がポリプロピレン粒子、ポリエチレン粒子、およびプロピレン－エチレン共重合樹脂粒子よりなる群から選択される少なくとも１つである、＜１＞～＜３＞のいずれか１つに記載の耐水性紙。
＜５＞ 耐水性層中の有機粒子の含有量が０．５質量％以上である、＜１＞～＜４＞のいずれか１つに記載の耐水性紙。
＜６＞ 有機粒子が水分散性の有機粒子である、＜１＞～＜５＞のいずれか１つに記載の耐水性紙。
＜７＞ 耐水性層の塗工量が０．１ｇ／ｍ２以上２０ｇ／ｍ２以下である、＜１＞～＜６＞のいずれか１つに記載の耐水性紙。
＜８＞ 紙基材の少なくとも一方の面に、少なくとも１層の下塗り層、および耐水性層をこの順に有する、＜１＞～＜７＞のいずれか１つに記載の耐水性紙。
＜９＞ 前記下塗り層が、エチレン－メタクリル酸共重合体を含有する、＜８＞に記載の耐水性紙。
＜１０＞ 透気度が１，０００秒以上である、＜１＞～＜９＞のいずれか１つに記載の耐水性紙。
＜１１＞ 耐水性層を設けた面の測定時間３０分間における２０℃の水に対するＣｏｂｂ吸水度が４０ｇ／ｍ２以下である、＜１＞～＜１０＞のいずれか１つに記載の耐水性紙。
＜１２＞ 耐水性層を設けた面の測定時間３０分間における９０℃の水に対するＣｏｂｂ吸水度が１００ｇ／ｍ２以下である、＜１＞～＜１１＞のいずれか１つに記載の耐水性紙。
＜１３＞ ヒートシール性を有する、＜１＞～＜１２＞のいずれか１つに記載の耐水性紙。
＜１４＞ 液体容器、またはその蓋用である、＜１＞～＜１３＞のいずれか１つに記載の耐水性紙。
＜１５＞ ＜１＞～＜１４＞のいずれか１つに記載の耐水性紙を用いてなる、液体容器、またはその蓋。
＜１６＞ 液体容器が紙コップである、＜１５＞に記載の液体容器、またはその蓋。
The present inventors have found that by blending an ethylene-methacrylic acid copolymer in the water-resistant layer and further blending a specific amount of organic particles having a specific melting point or softening point, excellent water resistance and blocking resistance can be obtained. and that a water-resistant paper having excellent heat-sealing properties can be obtained. The present invention relates to the following <1> to <16>.
<1> A water-resistant paper having a water-resistant layer as the uppermost layer on at least one surface of a paper substrate, wherein the water-resistant layer contains an ethylene-methacrylic acid copolymer and organic particles, and the organic particles A water-resistant paper having a melting point or softening point of 100° C. or higher and a content of organic particles in the water-resistant layer of 40% by mass or less.
<2> The water-resistant paper according to <1>, wherein the organic particles have an average particle size of 0.01 μm or more and 50 μm or less.
<3> The water-resistant paper according to <1> or <2>, wherein the organic particles are polyolefin particles.
<4> The water resistance according to any one of <1> to <3>, wherein the organic particles are at least one selected from the group consisting of polypropylene particles, polyethylene particles, and propylene-ethylene copolymer resin particles. paper.
<5> The water-resistant paper according to any one of <1> to <4>, wherein the content of organic particles in the water-resistant layer is 0.5% by mass or more.
<6> The water-resistant paper according to any one of <1> to <5>, wherein the organic particles are water-dispersible organic particles.
<7> The water-resistant paper according to any one of <1> to <6>, wherein the coating amount of the water-resistant layer is 0.1 g/m 2 or more and 20 g/m 2 or less.
<8> The water-resistant paper according to any one of <1> to <7>, which has at least one undercoat layer and a water-resistant layer in this order on at least one surface of the paper substrate.
<9> The water-resistant paper according to <8>, wherein the undercoat layer contains an ethylene-methacrylic acid copolymer.
<10> The water-resistant paper according to any one of <1> to <9>, which has an air permeability of 1,000 seconds or more.
<11> The water resistance according to any one of <1> to <10>, wherein the surface provided with the water resistant layer has a Cobb water absorbency of 40 g/m 2 or less with respect to water at 20° C. for 30 minutes. paper.
<12> The water resistance according to any one of <1> to <11>, wherein the surface provided with the water resistant layer has a Cobb water absorbency of 100 g/m 2 or less in water at 90°C for 30 minutes. paper.
<13> The water-resistant paper according to any one of <1> to <12>, which has heat-sealing properties.
<14> The waterproof paper according to any one of <1> to <13>, which is used for a liquid container or its lid.
<15> A liquid container or a lid thereof, using the water-resistant paper according to any one of <1> to <14>.
<16> The liquid container or its lid according to <15>, wherein the liquid container is a paper cup.
本発明によれば、耐水性に優れるとともに、耐ブロッキング性およびヒートシール性に優れた耐水性紙を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, while being excellent in water resistance, the water resistant paper excellent in blocking resistance and heat-sealing property can be provided.
［耐水性紙］
本実施形態の耐水性紙は、紙基材の少なくとも一方の面の最上層に耐水性層を有する耐水性紙であり、該耐水性層が、エチレン－メタクリル酸共重合体、および有機粒子を含有し、該有機粒子の融点または軟化点が１００℃以上であり、耐水性層中の有機粒子の含有量が４０質量％以下である。
実施形態によれば、耐水性に優れるとともに、耐ブロッキング性およびヒートシール性に優れた耐水性紙を提供することができる。
上述した効果が得られる詳細な理由は不明であるが、一部は以下のように考えられる。本実施形態では、耐水性層にエチレン－メタクリル酸共重合体が配合されており、これにより、優れた耐水性およびヒートシール性を有するものと考えられる。また、耐水性層にさらに特定の融点または軟化点を有する有機粒子を、特定量配合することにより、耐水性およびヒートシール性を劣化させることなく、耐水性層の表面が粗面化され、耐水性紙を重ね合わせた際に、耐水性層の耐水性紙の裏面への貼り付きを抑制し、耐ブロッキング性に優れた耐水性紙が得られたものと考えられる。
また、耐水性紙の製造工程において、紙基材の表面および裏面に塗工層を設ける場合、片面に塗工、乾燥して塗工層を設けて、巻き取った後、巻き出して、もう一方の面に塗工、乾燥して塗工層を設けることが一般的である。この時、後段の塗工、乾燥工程において、前段で塗工された塗工層が、金属ロールで摩擦されることにより、ロール汚れが発生するという問題があった。本実施形態において、前段で設ける塗工層の最上層を耐水性層とすることによって、両面塗工時のロール汚れの発生を抑制することができるという効果をも有する。
以下、本実施形態についてさらに詳細に説明する。
[Water resistant paper]
The water-resistant paper of the present embodiment is water-resistant paper having a water-resistant layer as the uppermost layer on at least one surface of the paper substrate, and the water-resistant layer contains an ethylene-methacrylic acid copolymer and organic particles. The melting point or softening point of the organic particles is 100° C. or higher, and the content of the organic particles in the water-resistant layer is 40% by mass or less.
According to the embodiments, it is possible to provide water-resistant paper that is excellent in water resistance, blocking resistance, and heat-sealing property.
Although the detailed reason why the above effect is obtained is unknown, part of it is considered as follows. In this embodiment, the water-resistant layer contains an ethylene-methacrylic acid copolymer, which is considered to provide excellent water resistance and heat-sealing properties. Further, by adding a specific amount of organic particles having a specific melting point or softening point to the water-resistant layer, the surface of the water-resistant layer can be roughened without deteriorating the water resistance and heat-sealing properties. It is considered that the water-resistant paper having excellent anti-blocking property was obtained by suppressing sticking of the water-resistant layer to the back surface of the water-resistant paper when the adhesive paper was superimposed.
In addition, in the manufacturing process of water-resistant paper, when a coating layer is provided on the front and back sides of the paper substrate, one side is coated and dried to provide a coating layer, and after winding, unwinding, Generally, one surface is coated and dried to form a coating layer. At this time, in the subsequent coating and drying steps, there is a problem that the coating layer coated in the previous stage is rubbed with a metal roll, resulting in roll contamination. In this embodiment, by making the uppermost layer of the coating layer provided in the preceding stage a water-resistant layer, there is also the effect of being able to suppress the occurrence of roll contamination during double-sided coating.
The present embodiment will be described in further detail below.
＜耐水性層＞
本実施形態において、耐水性紙は、紙基材の少なくとも一方の面の最上層に、エチレン－メタクリル酸共重合体および有機粒子を含有する耐水性層を有する。
なお、本実施形態の耐水性紙は、耐水性層を紙基材の両方の面に有していてもよい。
<Water resistant layer>
In this embodiment, the water-resistant paper has a water-resistant layer containing an ethylene-methacrylic acid copolymer and organic particles as the uppermost layer on at least one surface of the paper substrate.
The water-resistant paper of this embodiment may have water-resistant layers on both sides of the paper substrate.
〔エチレン－メタクリル酸共重合体〕
本実施形態において、耐水性層は、エチレン－メタクリル酸共重合体を含有する。
本発明者等は、鋭意検討した結果、耐水性層がエチレン－メタクリル酸共重合体を含有することにより、優れた耐水性が得られることを見出した。また、他の効果としてエチレン－メタクリル酸共重合体を配合することにより、ヒートシール性にも優れた耐水性紙が得られる。
ここで、エチレン－メタクリル酸共重合体は、アイオノマーとして配合されていてもよい。なお、「アイオノマーとして配合される」とは、少なくとも耐水性層を作製する際に、その原料としてアイオノマーが使用されていることを意味し、製造後において、耐水性層がアイオノマーの形で樹脂を含有していなくてもよい。
アイオノマーとは、高分子を陽イオンで中和したものである。すなわち、エチレン－メタクリル酸共重合体を陽イオンで中和した樹脂は、全てアイオノマーに該当する。陽イオンとしては、金属イオンの他、アンモニウムイオン（ＮＨ４
＋）、有機アンモニウムイオンが例示される。金属イオンとしては、リチウムイオン（Ｌｉ＋）、ナトリウムイオン（Ｎａ＋）、カリウムイオン（Ｋ＋）等のアルカリ金属イオン、マグネシウムイオン（Ｍｇ２＋）、カルシウムイオン（Ｃａ２＋）等のアルカリ土類金属イオン、亜鉛イオン（Ｚｎ２＋）、銅イオン（Ｃｕ２＋）等の遷移金属イオン等が例示される。これらの中でも、入手容易性等の観点から、金属イオンとしては、ナトリウムイオンが好ましい。
[Ethylene-methacrylic acid copolymer]
In this embodiment, the water-resistant layer contains an ethylene-methacrylic acid copolymer.
As a result of intensive studies, the inventors of the present invention have found that excellent water resistance can be obtained by including an ethylene-methacrylic acid copolymer in the water-resistant layer. In addition, as another effect, by blending ethylene-methacrylic acid copolymer, water-resistant paper having excellent heat-sealing properties can be obtained.
Here, the ethylene-methacrylic acid copolymer may be blended as an ionomer. Note that the phrase "blended as an ionomer" means that an ionomer is used as a raw material at least when the water-resistant layer is produced, and after production, the water-resistant layer contains a resin in the form of an ionomer. It does not have to be contained.
Ionomers are polymers neutralized with cations. That is, all resins obtained by neutralizing ethylene-methacrylic acid copolymers with cations correspond to ionomers. Examples of cations include metal ions, ammonium ions (NH 4 + ), and organic ammonium ions. Examples of metal ions include alkali metal ions such as lithium ions (Li + ), sodium ions (Na + ) and potassium ions (K + ); alkaline earth metal ions such as magnesium ions (Mg 2+ ) and calcium ions (Ca 2+ ); ions, zinc ions (Zn 2+ ), copper ions (Cu 2+ ) and other transition metal ions, and the like. Among these, the sodium ion is preferable as the metal ion from the viewpoint of availability and the like.
エチレン－メタクリル酸としては、市販されている製品を使用してもよく、例えば、三井化学のケミパールシリーズ（Ｓ－１００、Ｓ－３００、Ｓ－５００）、丸芳化学株式会社製のＭＹＥ－３０ＥＲ、ＭＹＥ－３０ＭＡＺ、デュポン社製のサーリンシリーズ、三井・デュポン・ポリケミカル社製のハイミランシリーズ、東邦化学工業株式会社製のハイテックＳＣ－１００、中央理化工業株式会社製のアクアテックスＡＣ－３１００が例示される。 As ethylene-methacrylic acid, commercially available products may be used, for example, Mitsui Chemicals Chemipearl series (S-100, S-300, S-500), Maruyoshi Chemical Co., Ltd. MYE- 30ER, MYE-30MAZ, Surlyn series manufactured by DuPont, Himilan series manufactured by Mitsui DuPont Polychemical, Hitec SC-100 manufactured by Toho Chemical Industry Co., Ltd., Aquatex AC-3100 manufactured by Chuo Rika Kogyo Co., Ltd. is exemplified.
エチレン－メタクリル酸の耐水性層中での含有量は、耐水性、特に熱水に対する耐水性、およびヒートシール性の観点から、好ましくは５０質量％以上、より好ましくは６０質量％以上、さらに好ましくは７０質量％以上であり、そして、耐ブロッキング性の観点から、好ましくは９９質量％以下、より好ましくは９８質量％以下、さらに好ましくは９７質量％以下である。 The content of ethylene-methacrylic acid in the water-resistant layer is preferably 50% by mass or more, more preferably 60% by mass or more, more preferably 60% by mass or more, from the viewpoint of water resistance, particularly water resistance to hot water, and heat sealability. is 70% by mass or more, and is preferably 99% by mass or less, more preferably 98% by mass or less, and still more preferably 97% by mass or less from the viewpoint of blocking resistance.
〔有機粒子〕
本実施形態において、耐水性層は、上記エチレン－メタクリル酸共重合体に加えて、有機粒子を含有する。
有機粒子は、融点または軟化点が１００℃以上である。有機粒子の融点または軟化点が１００℃以上であると、乾燥時に有機粒子が溶融または軟化することなく、優れたブロッキング性が得られる。さらに、上記のロール汚れを抑制することができる。また、融点または軟化点が１００℃以上である有機粒子を含有させると、耐水性が向上する。その理由は不明であるが、エチレン－メタクリル酸共重合体と有機粒子の融点（または軟化点）差により、エチレン－メタクリル酸共重合体の成膜時に生じる亀裂が、後から溶融する有機粒子で埋まり、耐水性層のクラックおよびピンホールが低減するためと考えられる。ただし、本発明の効果は、上記メカニズムによって制限されるものではない。
融点または軟化点は、好ましくは１１０℃以上、より好ましくは１２０℃以上、さらに好ましくは１２５℃以上であり、上限は特に限定されないが、好ましくは２４０℃以下、より好ましくは２００℃以下、さらに好ましくは１６０℃以下である。
有機粒子の融点または軟化点は、環球法軟化点、ＪＩＳ Ｋ２２０７：２００６により測定される。
[Organic particles]
In this embodiment, the water-resistant layer contains organic particles in addition to the ethylene-methacrylic acid copolymer.
The organic particles have a melting point or softening point of 100° C. or higher. When the melting point or softening point of the organic particles is 100° C. or higher, excellent blocking properties can be obtained without the organic particles melting or softening during drying. Furthermore, the roll contamination mentioned above can be suppressed. In addition, when organic particles having a melting point or softening point of 100° C. or higher are contained, the water resistance is improved. The reason for this is unknown, but due to the difference in the melting point (or softening point) between the ethylene-methacrylic acid copolymer and the organic particles, the cracks that occur during the film formation of the ethylene-methacrylic acid copolymer are caused by the organic particles that melt later. This is believed to be due to the fact that cracks and pinholes in the water-resistant layer are reduced. However, the effects of the present invention are not limited by the above mechanism.
The melting point or softening point is preferably 110°C or higher, more preferably 120°C or higher, and still more preferably 125°C or higher, and the upper limit is not particularly limited, but is preferably 240°C or lower, more preferably 200°C or lower, and still more preferably is below 160°C.
The melting point or softening point of the organic particles is measured by ring and ball method softening point, JIS K2207:2006.
有機粒子は、耐水性層用塗工液を水系塗工液とすることが好ましい観点から、水分散性の有機粒子であることが好ましい。すなわち、有機粒子は、水分散液として耐水性層用塗工液に配合されることが好ましい。また、ヒートシール性、耐水性を向上させる観点から、有機粒子の水分散液は、界面活性剤、分散剤等の使用が少ない、または使用されていないことが好ましい。
有機粒子は、例えば、ポリエステル粒子、アクリル粒子、ポリスチレン粒子、ナイロン粒子、シリコーン粒子、ポリオレフィン粒子等が挙げられるが、上記の観点から、ポリオレフィン粒子であることが好ましい。
ポリオレフィン粒子を構成するポリオレフィン樹脂としては、エチレン、プロピレン、１－ブテン、１－ペンテン、１－ヘキセンなどのオレフィンの重合体を挙げることができる。ポリオレフィン樹脂は、上記例示したオレフィンの単独重合体であってもよいし、共重合体であってもよい。また、ポリオレフィン樹脂は変性されていてもよい。なお、変性としては、例えば、アニオン変性、カチオン変性などが例示され、変性による水への分散性が向上したポリオレフィン粒子を使用することも好ましい。
ポリオレフィン粒子は、ポリエチレン粒子、ポリプロピレン粒子、およびプロピレン－エチレン共重合体樹脂粒子よりなる群から選択される少なくとも１つであることがより好ましい。
ポリエチレンは、高密度ポリエチレン、低密度ポリエチレンであってもよく、ポリプロピレンは高密度ポリプロピレン、低密度ポリプロピレンであってもよく、特に限定されない。
The organic particles are preferably water-dispersible organic particles from the viewpoint that the water-resistant layer coating liquid is preferably an aqueous coating liquid. That is, the organic particles are preferably blended in the water-resistant layer coating liquid as an aqueous dispersion. From the viewpoint of improving heat-sealing properties and water resistance, it is preferable that the aqueous dispersion of organic particles contain little or no surfactant, dispersant, or the like.
Examples of organic particles include polyester particles, acrylic particles, polystyrene particles, nylon particles, silicone particles, polyolefin particles, etc. From the above viewpoints, polyolefin particles are preferable.
Examples of polyolefin resins constituting polyolefin particles include polymers of olefins such as ethylene, propylene, 1-butene, 1-pentene and 1-hexene. The polyolefin resin may be a homopolymer or a copolymer of the olefins exemplified above. Moreover, the polyolefin resin may be modified. Modification includes, for example, anion modification and cation modification, and it is also preferable to use polyolefin particles improved in dispersibility in water by modification.
More preferably, the polyolefin particles are at least one selected from the group consisting of polyethylene particles, polypropylene particles, and propylene-ethylene copolymer resin particles.
Polyethylene may be high-density polyethylene or low-density polyethylene, polypropylene may be high-density polypropylene or low-density polypropylene, and is not particularly limited.
有機粒子の形状は特に限定されないが、球状であることが好ましい。
有機粒子の平均粒径は、耐ブロッキング性の観点から、好ましくは０．０１μｍ以上、より好ましくは０．０２μｍ以上、さらに好ましくは０．０３μｍ以上であり、そして、ヒートシール性維持の観点から、好ましくは５０μｍ以下、より好ましくは３０μｍ以下、さらに好ましくは１５μｍ以下、よりさらに好ましくは１０μｍ以下である。
なお、有機粒子の平均粒径が耐水性層の膜厚よりも大きいか、同程度であると、塗膜表面に凹凸が形成され、その結果、耐ブロッキング性に優れ、また、ロール汚れが抑制される。上記理由からは、有機粒子の平均粒径は、好ましくは１μｍ以上、より好ましくは３μｍ以上、さらに好ましくは５μｍ以上である。
また、有機粒子の平均粒径が膜厚よりも小さく、例えば、１．０μｍ未満であると、耐水性層を設ける際に、耐水性層用塗工液に含まれる水分の蒸発とともに有機粒子が塗膜表面に配向し、耐水性層表面を保護するため、耐ブロッキング性に優れ、また、ロール汚れが抑制される。上記理由からは、有機粒子の平均粒径は、好ましくは０．５μｍ以下、より好ましくは０．３μｍ以下、さらに好ましくは０．１μｍ以下である。
有機粒子の平均粒径は、レーザー回折法の原理によるレーザー回折式粒度分布測定装置やコールカウンター法により測定される。
Although the shape of the organic particles is not particularly limited, it is preferably spherical.
The average particle size of the organic particles is preferably 0.01 μm or more, more preferably 0.02 μm or more, and still more preferably 0.03 μm or more from the viewpoint of blocking resistance. It is preferably 50 μm or less, more preferably 30 μm or less, still more preferably 15 μm or less, and even more preferably 10 μm or less.
If the average particle size of the organic particles is larger than or about the same as the film thickness of the water-resistant layer, unevenness is formed on the surface of the coating film, resulting in excellent blocking resistance and suppression of roll staining. be done. For the above reasons, the average particle size of the organic particles is preferably 1 μm or more, more preferably 3 μm or more, and even more preferably 5 μm or more.
Further, when the average particle size of the organic particles is smaller than the film thickness, for example, less than 1.0 μm, the organic particles evaporate as the water contained in the water-resistant layer coating liquid evaporates when the water-resistant layer is formed. Since it is oriented on the surface of the coating film and protects the surface of the water-resistant layer, it has excellent blocking resistance and suppresses roll staining. For the above reasons, the average particle size of the organic particles is preferably 0.5 μm or less, more preferably 0.3 μm or less, and even more preferably 0.1 μm or less.
The average particle size of the organic particles is measured by a laser diffraction particle size distribution analyzer or a Coal counter method based on the principle of laser diffraction.
耐水性層中の有機粒子の含有量は、耐ブロッキング性の観点から、好ましくは０．５質量％以上、より好ましくは１．０質量％以上、さらに好ましくは１．５質量％以上であり、そして、ヒートシール性の観点から、４０質量％以下であり、好ましくは３５質量％以下、より好ましくは３０質量％以下、さらに好ましくは２５質量％以下、よりさらに好ましくは１５質量％以下、特に好ましくは１０質量％以下である。
耐水性層中のエチレン－メタクリル酸共重合体と有機粒子の含有量の質量比（エチレン－メタクリル酸共重合体／有機粒子）は、耐ブロッキング性および耐水性に向上の観点から、好ましくは６０／４０以上、より好ましくは７０／３０以上、さらに好ましくは７５／２５以上であり、そして、好ましくは９９．５／０．５以下、より好ましくは９９／１以下、さらに好ましくは９８／２以下である。
The content of the organic particles in the water-resistant layer is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and still more preferably 1.5% by mass or more, from the viewpoint of blocking resistance. From the viewpoint of heat-sealability, it is 40% by mass or less, preferably 35% by mass or less, more preferably 30% by mass or less, even more preferably 25% by mass or less, even more preferably 15% by mass or less, and particularly preferably is 10% by mass or less.
The mass ratio of the content of the ethylene-methacrylic acid copolymer and the organic particles in the water-resistant layer (ethylene-methacrylic acid copolymer/organic particles) is preferably 60 from the viewpoint of improving blocking resistance and water resistance. /40 or more, more preferably 70/30 or more, still more preferably 75/25 or more, and preferably 99.5/0.5 or less, more preferably 99/1 or less, further preferably 98/2 or less is.
耐水性層には、上述したエチレン－メタクリル酸共重合体および有機粒子に加えて、他の成分を添加してもよい。
他の成分としては、例えば、消泡剤；粘度調整剤；界面活性剤、アルコール等のレベリング剤；着色染料等の着色剤などが例示される。
これらの中でも、泡立ちによる層内への気泡の混入を抑制する観点から、他の成分として消泡剤を含有することが好ましい。消泡剤は市販されている製品の中から適宜選択してもよく、具体的には、株式会社日新化学研究所製の各種消泡剤が例示される。
消泡剤の添加量は特に限定されないが、エチレン－メタクリル酸共重合体（固形分量）１００質量部に対して、好ましくは０．１質量部以上３．０質量部以下である。
なお、これらの他の成分は、耐水性およびヒートシール性を悪化させる傾向があることから、他の成分の含有量の合計は、耐水性層の固形分中、好ましくは５０質量％以下、より好ましくは３０質量％以下、さらに好ましくは１０質量％以下である。
In addition to the ethylene-methacrylic acid copolymer and organic particles described above, other components may be added to the water-resistant layer.
Examples of other components include antifoaming agents; viscosity modifiers; leveling agents such as surfactants and alcohols; coloring agents such as coloring dyes.
Among these, it is preferable to contain an antifoaming agent as another component from the viewpoint of suppressing air bubbles from being mixed into the layer due to foaming. The antifoaming agent may be appropriately selected from commercially available products, and specific examples include various antifoaming agents manufactured by Nisshin Chemical Laboratory Co., Ltd.
The amount of the antifoaming agent to be added is not particularly limited, but is preferably 0.1 parts by mass or more and 3.0 parts by mass or less with respect to 100 parts by mass of the ethylene-methacrylic acid copolymer (solid content).
In addition, since these other components tend to deteriorate the water resistance and heat sealability, the total content of the other components is preferably 50% by mass or less in the solid content of the water resistant layer, and more It is preferably 30% by mass or less, more preferably 10% by mass or less.
耐水性層は、エチレン－メタクリル酸共重合体および有機粒子を含有する耐水性層用塗工液を調製し、これを、紙基材の少なくとも一方の面に塗工することにより得られる。
耐水性層用塗工液は、自己乳化型ディスパーションであることが好ましい。すなわち、耐水性層用塗工液は、界面活性剤等の乳化剤、分散剤を含有しないことが好ましい。
The water-resistant layer is obtained by preparing a water-resistant layer coating solution containing an ethylene-methacrylic acid copolymer and organic particles, and applying the solution to at least one side of the paper substrate.
The water-resistant layer coating liquid is preferably a self-emulsifying dispersion. That is, the water-resistant layer coating liquid preferably does not contain an emulsifier such as a surfactant or a dispersant.
耐水性層用塗工液を塗工する方法としては、特に限定されず、一般に使用されている塗工装置から適宜選択して使用すればよい。例えば、エアナイフコーター、ブレードコーター、グラビアコーター、ロッドブレードコーター、ロールコーター、リバースロールコーター、バーコーター、カーテンコーター、ダイスロットコーター、チャンプレックスコーター、メータリングブレード式のサイズプレスコーター、ショートドウェルコーター、スプレーコーター、ゲートロールコーター、リップコーター等の公知の各種塗工装置が挙げられる。 The method for applying the water-resistant layer coating liquid is not particularly limited, and may be appropriately selected from commonly used coating apparatuses. For example, air knife coater, blade coater, gravure coater, rod blade coater, roll coater, reverse roll coater, bar coater, curtain coater, die slot coater, Champlex coater, metering blade type size press coater, short dwell coater, spray Various known coating apparatuses such as a coater, a gate roll coater, and a lip coater can be used.
〔耐水性層の好ましい態様〕
本実施形態の耐水性紙は、紙基材の少なくとも一方の面の最上層に耐水性層を有していればよく、紙基材の両面に有することも好ましい。
耐水性層を両面に有することにより、例えば、結露が生じるような用途（例えば、冷水用紙コップ等）にも好適に適用可能となる。
[Preferred Embodiment of Water Resistant Layer]
The water-resistant paper of the present embodiment may have a water-resistant layer as the uppermost layer on at least one side of the paper base material, and preferably both sides of the paper base material.
By having water-resistant layers on both sides, for example, it can be suitably applied to applications where dew condensation occurs (for example, paper cups for cold water, etc.).
耐水性紙は、少なくとも一方の面の最上層に耐水性層を有する。紙基材の最上層にエチレン－メタクリル酸共重合体および顔料を含有する耐水性層を有することにより、耐水性およびヒートシール性が付与されるともに、耐ブロッキング性を付与することができる。
耐水性層の塗工量は、耐水性、ヒートシール性および耐ブロッキング性に優れる耐水性層とする観点から、好ましくは０．１ｇ／ｍ２以上、より好ましくは０．５ｇ／ｍ２以上、さらに好ましくは１．０ｇ／ｍ２以上、よりさらに好ましくは３．０ｇ／ｍ２以上であり、そして、好ましくは２０ｇ／ｍ２以下、より好ましくは１５ｇ／ｍ２以下、さらに好ましくは１０ｇ／ｍ２以下である。
耐水性層の膜厚は、耐水性、ヒートシール性および耐ブロッキング性に優れる耐水性層とする観点から、好ましくは０．１μｍ以上、より好ましくは０．５μｍ以上、さらに好ましくは１．０μｍ以上、よりさらに好ましくは３．０μｍ以上であり、そして、好ましくは２０μｍ以下、より好ましくは１５μｍ以下、さらに好ましくは１０μｍ以下である。
The water-resistant paper has a water-resistant layer as the top layer on at least one side. By having a water-resistant layer containing an ethylene-methacrylic acid copolymer and a pigment as the uppermost layer of the paper base material, water resistance and heat-sealing properties can be imparted, and blocking resistance can be imparted.
The coating amount of the water-resistant layer is preferably 0.1 g/m 2 or more, more preferably 0.5 g/m 2 or more, from the viewpoint of providing a water-resistant layer having excellent water resistance, heat sealability and blocking resistance. More preferably 1.0 g/m 2 or more, still more preferably 3.0 g/m 2 or more, and preferably 20 g/m 2 or less, more preferably 15 g/m 2 or less, still more preferably 10 g/m 2 2 or less.
The film thickness of the water-resistant layer is preferably 0.1 μm or more, more preferably 0.5 μm or more, and still more preferably 1.0 μm or more, from the viewpoint of making the water-resistant layer excellent in water resistance, heat-sealing property and blocking resistance. , more preferably 3.0 μm or more, and preferably 20 μm or less, more preferably 15 μm or less, still more preferably 10 μm or less.
＜その他の層＞
本実施形態において、耐水性紙は、耐水性をより向上させる観点から、耐水性層の下層に、下塗り層を有することが好ましい。すなわち、耐水性紙は、紙基材上に、下塗り層および耐水性層をこの順で有することが好ましい。下塗り層を設けることにより、耐水性をより向上させることができるとともに、ヒートシール性をも向上させることができるので好ましい。また、下塗り層を設けることにより、紙基材との密着性の向上も期待される。
下塗り層としては、耐水性やヒートシール性の付与を目的とする下塗り耐水性層、目止めや印刷適性の向上を目的として付与する顔料塗工層が例示される。
<Other layers>
In this embodiment, the water-resistant paper preferably has an undercoat layer below the water-resistant layer from the viewpoint of further improving water resistance. That is, the water-resistant paper preferably has an undercoat layer and a water-resistant layer in this order on a paper substrate. By providing an undercoat layer, the water resistance can be further improved, and the heat-sealing property can also be improved, which is preferable. In addition, by providing the undercoat layer, it is expected to improve the adhesion to the paper substrate.
Examples of the undercoat layer include a water-resistant undercoat layer for the purpose of imparting water resistance and heat sealability, and a pigment coating layer for the purpose of improving filling and printability.
〔下塗り耐水性層〕
下塗り耐水性層は、エチレン－メタクリル酸共重合体を含有することが好ましく、エチレン－メタクリル酸共重合体としては、耐水性層の成分として上述したものが例示される。すなわち、下塗り耐水性層に配合されるエチレン－メタクリル酸は、エチレン－メタクリル酸共重合体アイオノマーであってもよく、例えば、エチレン－メタクリル酸共重合体の金属塩、エチレン－メタクリル酸共重合体のアンモニウム塩であってもよい。
下塗り耐水性層は、エチレン－メタクリル酸に加えて、上記耐水性層で例示したその他の成分が配合されていてもよい。
下塗り耐水性層は、上記耐水性層から有機粒子を除いた配合であることも好ましいが、その場合、べたつきが悪いことから、ロールが汚れ、塗工が困難になる可能性がある。上記の現象を抑制し、操業の安定性を向上させる観点からは、下塗り耐水性層には、エチレン－メタクリル酸共重合体に加えて、有機粒子を配合することも好ましい。下塗り耐水性層に配合される有機粒子としては、耐水性層の成分として上述したものが例示される。有機粒子の平均粒径、融点または軟化点の好ましい範囲も上述の通りである。下塗り耐水性層にエチレン－メタクリル酸共重合体および有機粒子が配合されている場合において、下塗り耐水性層中のエチレン－メタクリル酸共重合体および有機粒子の配合量の質量比（エチレン－メタクリル酸共重合体／有機粒子）は、耐水性および耐ブロッキング性の観点からは、耐ブロッキング性および耐水性向上の観点から、好ましくは６０／４０以上、より好ましくは７０／３０以上、さらに好ましくは７５／２５以上であり、そして、好ましくは９９．５／０．５以下、より好ましくは９９／１以下、さらに好ましくは９８／２以下である。
[Undercoat water-resistant layer]
The water-resistant undercoat layer preferably contains an ethylene-methacrylic acid copolymer, and examples of the ethylene-methacrylic acid copolymer include those mentioned above as components of the water-resistant layer. That is, the ethylene-methacrylic acid blended in the undercoat water-resistant layer may be an ethylene-methacrylic acid copolymer ionomer, such as a metal salt of an ethylene-methacrylic acid copolymer, an ethylene-methacrylic acid copolymer may be an ammonium salt of
The water-resistant undercoat layer may contain, in addition to ethylene-methacrylic acid, other components exemplified for the water-resistant layer.
It is also preferable that the water-resistant undercoat layer has a composition obtained by removing the organic particles from the water-resistant layer. From the viewpoint of suppressing the above phenomenon and improving operational stability, it is also preferable to blend organic particles in the undercoat water-resistant layer in addition to the ethylene-methacrylic acid copolymer. Examples of the organic particles to be blended in the undercoat water-resistant layer include those described above as components of the water-resistant layer. The preferred ranges of the average particle size, melting point, or softening point of the organic particles are also as described above. When the ethylene-methacrylic acid copolymer and organic particles are blended in the water-resistant undercoat layer, the mass ratio of the ethylene-methacrylic acid copolymer and the organic particles in the water-resistant undercoat layer (ethylene-methacrylic acid from the viewpoint of water resistance and blocking resistance, preferably 60/40 or more, more preferably 70/30 or more, still more preferably 75 /25 or more, and preferably 99.5/0.5 or less, more preferably 99/1 or less, and even more preferably 98/2 or less.
下塗り耐水性層の塗工量は、耐水性向上および耐水性層の塗工量減少の観点から、好ましくは１．０ｇ／ｍ２以上、より好ましくは２．０ｇ／ｍ２以上、さらに好ましくは２．５ｇ／ｍ２以上であり、そして、好ましくは２０ｇ／ｍ２以下、より好ましくは１５ｇ／ｍ２以下、さらに好ましくは１０ｇ／ｍ２以下、よりさらに好ましくは８．０ｇ／ｍ２以下である。 The coating amount of the undercoat water-resistant layer is preferably 1.0 g/m 2 or more, more preferably 2.0 g/m 2 or more, and still more preferably from the viewpoint of improving water resistance and reducing the coating amount of the water-resistant layer. 2.5 g/m 2 or more, and preferably 20 g/m 2 or less, more preferably 15 g/m 2 or less, even more preferably 10 g/m 2 or less, and even more preferably 8.0 g/m 2 or less. be.
〔顔料塗工層〕
本実施形態の耐水性紙は、紙基材と耐水性層との間、または紙基材と下塗り耐水性層との間に、顔料塗工層を有していてもよい。紙基材を目止めし、平滑化させることができる。これにより、均一な下塗り耐水性層および耐水性層を形成でき、耐水性およびヒートシール性が向上する。
[Pigment coating layer]
The water-resistant paper of this embodiment may have a pigment coating layer between the paper base and the water-resistant layer or between the paper base and the undercoat water-resistant layer. The paper substrate can be sealed and smoothed. As a result, a uniform water-resistant undercoat layer and water-resistant layer can be formed, and the water resistance and heat-sealing properties are improved.
前記顔料塗工層は、主に顔料およびバインダーから構成される。なお、「顔料塗工層が主に顔料およびバインダーから構成される」とは、顔料塗工層中の顔料およびバインダーの合計含有量が、例えば５０質量％以上、好ましくは６０質量％以上、より好ましくは７０質量％以上、さらに好ましくは８０質量％以上、よりさらに好ましくは９０質量％以上、特に好ましくは９５質量％以上であることを意味する。上限は、特に限定されないが、１００質量％以下である。なお、顔料塗工層は、顔料およびバインダー以外に、任意の成分をさらに含んでいてもよい。
顔料塗工層に含まれる顔料としては、特に限定されないが、カオリン、タルク、マイカなどが挙げられる。
顔料の平均粒径は特に限定されないが、好ましくは０．０３μｍ以上、より好ましくは０．１μｍ以上、さらに好ましくは０．５μｍ以上であり、そして、好ましくは３０μｍ以下、より好ましくは１０μｍ以下、さらに好ましくは４μｍ以下である。顔料の平均粒径は、沈降法によって測定される値を採用するものとする。顔料が層状無機化合物であるとき、平均粒径は、平均長径を意味する。
顔料のアスペクト比は、好ましくは１０以上、より好ましくは２０以上、さらに好ましくは３０以上である。上限は、特に限定されないが、好ましくは１０，０００以下である。アスペクト比は、電子顕微鏡による観察やＸ線回折測定によって測定することができる。
顔料塗工層中の顔料の含有量は、好ましくは２０質量％以上、より好ましくは３０質量％以上、さらに好ましくは３５質量％以上であり、そして、好ましくは８０質量％以下、より好ましくは７０質量％以下、さらに好ましくは６０質量％以下である。
The pigment coating layer is mainly composed of a pigment and a binder. In addition, "the pigment coating layer is mainly composed of a pigment and a binder" means that the total content of the pigment and the binder in the pigment coating layer is, for example, 50% by mass or more, preferably 60% by mass or more, and more It means that the content is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and particularly preferably 95% by mass or more. Although the upper limit is not particularly limited, it is 100% by mass or less. The pigment coating layer may further contain optional components in addition to the pigment and the binder.
The pigment contained in the pigment coating layer is not particularly limited, but examples include kaolin, talc, mica, and the like.
Although the average particle size of the pigment is not particularly limited, it is preferably 0.03 μm or more, more preferably 0.1 μm or more, still more preferably 0.5 μm or more, and preferably 30 μm or less, more preferably 10 μm or less, and further preferably 0.5 μm or more. It is preferably 4 μm or less. For the average particle diameter of the pigment, a value measured by a sedimentation method shall be adopted. When the pigment is a layered inorganic compound, the average particle size means the average major axis.
The aspect ratio of the pigment is preferably 10 or more, more preferably 20 or more, still more preferably 30 or more. Although the upper limit is not particularly limited, it is preferably 10,000 or less. The aspect ratio can be measured by electron microscope observation or X-ray diffraction measurement.
The content of the pigment in the pigment coating layer is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 35% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass. % by mass or less, more preferably 60% by mass or less.
顔料塗工層に含まれるバインダーとしては、特に限定されないが、スチレン－ブタジエン系樹脂；アクリル酸メチル共重合体、メタクリル酸メチル共重合体、スチレン－アクリル共重合体、スチレン－メタクリル共重合体等のアクリル系樹脂；エチレン－アクリル酸共重合体、エチレン－メタクリル酸共重合体等のオレフィン・不飽和カルボン酸系共重合体；などが挙げられ、スチレン－ブタジエン系樹脂がより好ましい。
顔料塗工層中のバインダーの含有量は、好ましくは１０質量％以上、より好ましくは２０質量％以上、さらに好ましくは３０質量％以上であり、そして、好ましくは８０質量％以下、より好ましくは７０質量％以下、さらに好ましくは６５質量％以下である。
顔料塗工層の塗工量は、特に限定されないが、固形分で、好ましくは１ｇ／ｍ２以上、より好ましくは２ｇ／ｍ２以上であり、そして、好ましくは１０ｇ／ｍ２以下、より好ましくは５ｇ／ｍ２以下である。
顔料塗工層の形成方法は、特に限定されないが、顔料およびバインダーを含む分散液を紙基材上に塗工し、乾燥することで形成する方法が好ましい。
顔料および樹脂バインダーを含む分散液としては、水性分散液が好ましい。
顔料塗工層は、顔料およびバインダーに加えて、耐水性層において他の成分として例示した成分を含有していてもよく、消泡剤を含有することが好ましい。
The binder contained in the pigment coating layer is not particularly limited, but styrene-butadiene resin; methyl acrylate copolymer, methyl methacrylate copolymer, styrene-acrylic copolymer, styrene-methacrylic copolymer, etc. acrylic resins; olefin/unsaturated carboxylic acid copolymers such as ethylene-acrylic acid copolymers and ethylene-methacrylic acid copolymers; and the like, with styrene-butadiene resins being more preferred.
The binder content in the pigment coating layer is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass. % by mass or less, more preferably 65% by mass or less.
The coating amount of the pigment coating layer is not particularly limited, but the solid content is preferably 1 g/m 2 or more, more preferably 2 g/m 2 or more, and preferably 10 g/m 2 or less, more preferably. is 5 g/m 2 or less.
A method for forming the pigment coating layer is not particularly limited, but a method of coating a paper base material with a dispersion containing a pigment and a binder and drying the layer is preferable.
Aqueous dispersions are preferred as dispersions containing pigments and resin binders.
In addition to the pigment and the binder, the pigment-coated layer may contain the components exemplified as other components for the water-resistant layer, and preferably contains an antifoaming agent.
本実施形態の耐水性紙は、紙基材の両面に耐水性層を有していてもよく、例えば、第１の耐水性層、下塗り耐水性層、顔料塗工層、紙基材および第２の耐水性層がこの順に積層してなる構成を有していてもよい。
また、樹脂粒子を含有せず、耐水性およびヒートシール性を有する層を耐水性層を有する側とは反対面に有していてもよい。
The water-resistant paper of the present embodiment may have water-resistant layers on both sides of the paper base material, for example, a first water-resistant layer, a water-resistant undercoat layer, a pigment coating layer, a paper base material and a second water-resistant layer. It may have a structure in which two water-resistant layers are laminated in this order.
Also, a layer containing no resin particles and having water resistance and heat-sealing properties may be provided on the side opposite to the side having the water resistance layer.
＜紙基材＞
本実施形態の耐水性紙は、紙基材上の少なくとも一方の面の最上層に耐水性層を有する。
耐水性紙を食品容器用に使用する場合には、表層、裏層、および少なくとも１層以上の中層を有する多層紙とすることが好ましい。
紙基材を構成するパルプとしては、広葉樹晒クラフトパルプ（ＬＢＫＰ）、針葉樹晒クラフトパルプ（ＮＢＫＰ）等の化学パルプ；砕木パルプ（ＧＰ）、加圧式砕木パルプ（ＰＧＷ）、リファイナーメカニカルパルプ（ＲＭＰ）、サーモメカニカルパルプ（ＴＭＰ）、ケミサーモメカニカルパルプ（ＣＴＭＰ）、ケミメカニカルパルプ（ＣＭＰ）、ケミグランドパルプ（ＣＧＰ）等の機械パルプ；古紙パルプ；ケナフ、バガス、竹、コットン等の非木材繊維パルプ；合成パルプ等が挙げられる。これらのパルプは１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
<Paper substrate>
The water-resistant paper of this embodiment has a water-resistant layer as the uppermost layer on at least one surface of the paper substrate.
When water-resistant paper is used for food containers, it is preferable to use multi-layered paper having a surface layer, a back layer, and at least one middle layer.
Pulp constituting the paper substrate includes chemical pulp such as bleached hardwood kraft pulp (LBKP) and bleached softwood kraft pulp (NBKP); groundwood pulp (GP), pressurized groundwood pulp (PGW), and refiner mechanical pulp (RMP). , thermomechanical pulp (TMP), chemi-thermomechanical pulp (CTMP), chemi-mechanical pulp (CMP), chemi-grand pulp (CGP); waste paper pulp; non-wood fiber pulp such as kenaf, bagasse, bamboo, cotton, etc. ; Synthetic pulp and the like can be mentioned. These pulps may be used individually by 1 type, and may be used in combination of 2 or more types.
パルプの叩解度は、特に限定するものではないが、カナダ標準濾水度（ＣＳＦ）として、２００ｍＬ以上６５０ｍＬ以下が好ましく、３５０ｍＬ以上６００ｍＬ以下がより好ましい。パルプのＣＳＦが前記範囲内であれば、耐水性紙を液体容器原紙として使用する場合に、必要な紙力が得られやすい。２００ｍＬ以上であれば、繊維間結合が高くなりすぎず、成形加工での折り曲げ工程で、圧縮、引張などの応力が折り部の最表層に集中し、樹脂層が破壊される現象の発生を抑えることができ、良好な加工適性を維持することができる。また、６５０ｍＬ以下であれば、紙表面の平滑性が良好となり、印刷適性を維持することができる。
ＣＳＦは、ＪＩＳ Ｐ ８１２１－２：２０１２「パルプ－ろ水度試験方法－第２部：カナダ標準ろ水度法」に従って測定される。
The beating degree of the pulp is not particularly limited, but the Canadian Standard Freeness (CSF) is preferably 200 mL or more and 650 mL or less, more preferably 350 mL or more and 600 mL or less. If the CSF of the pulp is within the above range, the required paper strength can be easily obtained when the water-resistant paper is used as the base paper for liquid containers. If it is 200 mL or more, the bonding between fibers does not become too high, and stress such as compression and tension concentrates on the outermost layer of the folded part in the folding process in the molding process, suppressing the phenomenon of breaking the resin layer. and maintain good processability. Moreover, if it is 650 mL or less, the smoothness of the paper surface becomes favorable, and printability can be maintained.
CSF is measured according to JIS P 8121-2:2012 "Pulp - Freeness Test Method - Part 2: Canadian Standard Freeness Method".
紙基材への添加剤としては、例えばｐＨ調整剤（炭酸水素ナトリウム、水酸化ナトリウム等）、乾燥紙力剤（ポリアクリルアミド、澱粉等）、湿潤紙力剤（ポリアミドポリアミンエピクロロヒドリン樹脂、メラミン－ホルムアルデヒド樹脂、尿素－ホルムアルデヒド樹脂のいずれか）、内添サイズ剤（ロジン系、アルキルケテンダイマー等）、濾水歩留り向上剤、消泡剤、填料（炭酸カルシウム、タルク等）、染料等が挙げられる。これらの添加剤は１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。
添加剤の含有量は、特に限定されず、通常用いられている範囲であってよい。
Examples of additives to the paper substrate include pH adjusters (sodium hydrogen carbonate, sodium hydroxide, etc.), dry paper strength agents (polyacrylamide, starch, etc.), wet paper strength agents (polyamide polyamine epichlorohydrin resin, melamine-formaldehyde resin or urea-formaldehyde resin), internal sizing agents (rosin, alkylketene dimer, etc.), drainage retention improvers, antifoaming agents, fillers (calcium carbonate, talc, etc.), dyes, etc. mentioned. These additives may be used singly or in combination of two or more.
The content of the additive is not particularly limited, and may be within a commonly used range.
紙基材の坪量は、特に限定されないが、例えば紙コップ用途であれば、２００ｇ／ｍ２以上３５０ｇ／ｍ２以下が好ましい。
紙基材の坪量は、ＪＩＳ Ｐ ８１２４：２０１１に準拠して測定される。
紙基材の紙厚は、特に限定されないが、例えば紙コップ用途であれば、２５０μｍ以上４５０μｍ以下が好ましい。
紙基材の紙厚は、ＪＩＳ Ｐ ８１１８：２０１４に準拠して測定される。
The basis weight of the paper substrate is not particularly limited, but is preferably 200 g/m 2 or more and 350 g/m 2 or less for paper cup applications, for example.
The basis weight of the paper substrate is measured according to JIS P 8124:2011.
The paper thickness of the paper substrate is not particularly limited, but is preferably 250 μm or more and 450 μm or less for paper cup applications, for example.
The paper thickness of the paper substrate is measured according to JIS P 8118:2014.
〔紙基材の製造方法〕
紙基材を製造する方法としては、パルプを含有する紙料を抄紙する方法が挙げられる。なお、紙料は、添加剤をさらに含有してもよい。添加剤としては、例えば前記で挙げた添加剤が挙げられる。
紙料は、パルプスラリーに添加剤を添加することにより調製できる。
パルプスラリーは、パルプを水の存在下で叩解することにより得られる。パルプの叩解方法、叩解装置は特に限定されず、公知の叩解方法、叩解装置と同様であってよい。
紙料におけるパルプの含有量は、特に限定されず、通常用いられている範囲であってよい。例えば、紙料（固形分）の総質量に対して、６０質量％以上１００質量％未満である。
[Method for producing paper substrate]
As a method for producing a paper substrate, there is a method of making paper from a pulp-containing stock. The paper material may further contain additives. Examples of the additive include those listed above.
Stock can be prepared by adding additives to the pulp slurry.
Pulp slurry is obtained by beating pulp in the presence of water. The pulp beating method and beating apparatus are not particularly limited, and may be the same as known beating methods and beating apparatus.
The content of pulp in the stock is not particularly limited, and may be within a range commonly used. For example, it is 60% by mass or more and less than 100% by mass with respect to the total mass of the stock (solid content).
紙料の抄紙は定法により実施できる。例えば、紙料をワイヤ等に流延させ、脱水して湿紙を得て、必要に応じて複数の湿紙を重ね、この単層または多層の湿紙をプレスし、乾燥させる方法が挙げられる。このとき、複数の湿紙を重ねない場合は単層抄きの紙が得られ、複数の湿紙を重ねる場合は多層抄きの紙が得られる。
複数の湿紙を重ねる際に、湿紙の表面（他の湿紙を重ねる面）に接着剤を塗布してもよい。
Papermaking of stock can be carried out by a conventional method. For example, there is a method in which a paper stock is cast on a wire or the like, dewatered to obtain a wet paper web, a plurality of wet paper webs are stacked as necessary, and this single-layer or multi-layer wet paper web is pressed and dried. . At this time, when a plurality of wet paper webs are not stacked, a single-layer paper is obtained, and when a plurality of wet paper webs are stacked, a multi-layer paper is obtained.
When stacking a plurality of wet paper webs, an adhesive may be applied to the surface of the wet paper web (the surface on which other wet paper webs are stacked).
＜耐水性紙の物性＞
本実施形態の耐水性紙は、透気度が１，０００秒以上であることが好ましく、より好ましくは１０，０００秒以上、さらに好ましくは２５，０００秒以上、よりさらに好ましくは９９，９９９秒以上である。透気度の上限は、特に限定されないが、例えば１，０００，０００秒以下である。
透気度を上記範囲内とすることにより、空気を遮断する意味での遮断性が高くなり、耐水性にさらに優れる耐水性紙が得られる。特に、耐水性層を２層以上有する場合や、耐水性層の下層として顔料層を設けた場合には、透気度を高くすることができる。
透気度は、ＪＩＳ Ｐ ８１１７：２００９に準拠して測定される。
<Physical properties of water-resistant paper>
The water-resistant paper of the present embodiment preferably has an air permeability of 1,000 seconds or more, more preferably 10,000 seconds or more, still more preferably 25,000 seconds or more, and even more preferably 99,999 seconds. That's it. Although the upper limit of air permeability is not particularly limited, it is, for example, 1,000,000 seconds or less.
By setting the air permeability within the above range, the air-imperviousness of the paper is increased, and a water-resistant paper having even better water resistance can be obtained. In particular, when two or more water-resistant layers are provided, or when a pigment layer is provided as a lower layer of the water-resistant layer, the air permeability can be increased.
Air permeability is measured according to JIS P 8117:2009.
本実施形態の耐水性紙は、冷水への耐水性の観点から、耐水性層を設けた面の測定時間３０分における２０℃の水に対するＣｏｂｂ吸水度が、好ましくは４０ｇ／ｍ２以下、より好ましくは２０ｇ／ｍ２以下、さらに好ましくは１５ｇ／ｍ２以下、よりさらに好ましくは１０ｇ／ｍ２以下である。下限は特に限定されない。
Ｃｏｂｂ吸水度は、ＪＩＳ Ｐ ８１４０：１９９８に準拠して測定される。
From the viewpoint of water resistance to cold water, the water-resistant paper of the present embodiment preferably has a Cobb water absorbency of 40 g/m 2 or less, more than It is preferably 20 g/m 2 or less, more preferably 15 g/m 2 or less, still more preferably 10 g/m 2 or less. The lower limit is not particularly limited.
Cobb water absorbency is measured according to JIS P 8140:1998.
本実施形態の耐水性紙は、熱水への耐水性の観点から、耐水性層を設けた面の測定時間３０分における９０℃の水に対するＣｏｂｂ吸水度が、好ましくは１００ｇ／ｍ２以下、より好ましくは６０ｇ／ｍ２以下、さらに好ましくは３０ｇ／ｍ２以下、よりさらに好ましくは２０ｇ／ｍ２以下である。下限は特に限定されない。
Ｃｏｂｂ吸水度は、ＪＩＳ Ｐ ８１４０：１９９８に準拠して測定される。
From the viewpoint of water resistance to hot water, the water-resistant paper of the present embodiment preferably has a Cobb water absorbency of 100 g/m 2 or less for water at 90°C in a measurement time of 30 minutes on the surface provided with the water-resistant layer. It is more preferably 60 g/m 2 or less, still more preferably 30 g/m 2 or less, and even more preferably 20 g/m 2 or less. The lower limit is not particularly limited.
Cobb water absorbency is measured according to JIS P 8140:1998.
本実施形態の耐水性紙は、耐ブロッキング性に優れることが好ましく、６５℃において３０分間加熱後、圧力０．５ｋｇ／ｃｍ２で３０分間加圧し、冷却後に耐水性紙を剥離した際に、僅かに抵抗があるか、または抵抗なく剥がれることが好ましく、抵抗なく剥がれることがより好ましい。 The water - resistant paper of the present embodiment preferably has excellent blocking resistance. It is preferable that the adhesive be peeled off with little or no resistance, and more preferably be peeled off without resistance.
本実施形態の耐水性紙は、耐水性層がヒートシール性を有することが好ましい。
ヒートシールの条件は特に限定されないが、ヒートシール時の温度は例えば、６０℃以上３００℃以下であり、ヒートシール時の圧力は例えば０．０５ＭＰａ以上１０ＭＰａ以下であり、加圧時間は、例えば０．１秒以上１５秒以下である。
In the water-resistant paper of the present embodiment, the water-resistant layer preferably has heat-sealing properties.
The conditions for heat sealing are not particularly limited, but the temperature during heat sealing is, for example, 60° C. or higher and 300° C. or lower, the pressure during heat sealing is, for example, 0.05 MPa or higher and 10 MPa or lower, and the pressurization time is, for example, 0. .1 second or more and 15 seconds or less.
本実施形態の耐水性紙は、紙コップ等の液体容器またはその蓋、その他の耐水性が求められる紙器（例えば、紙トレー）に用いることが好ましい。液体容器に使用する場合には、耐水性層がヒートシール性を有することが成形性の観点から好ましい。
液体容器の成形の一例を挙げると、必要に応じて耐水性紙の表面、または裏面に印刷を施し、製造する液体容器の形状に対応した形状に打抜き加工し、折り曲げ加工し、重なり部分をヒートシールにより貼り合わせて液体容器とされる。
本実施形態の耐水性紙は、耐水性、ヒートシール性に優れるため、成形加工性にも優れる。
The water-resistant paper of the present embodiment is preferably used for liquid containers such as paper cups, their lids, and other paper containers that require water resistance (for example, paper trays). When used for a liquid container, the water-resistant layer preferably has heat-sealability from the viewpoint of formability.
To give an example of forming a liquid container, printing is applied to the surface or back of the water-resistant paper as necessary, punching into a shape corresponding to the shape of the liquid container to be manufactured, bending, and heating the overlapping part. A liquid container is formed by sticking together with a seal.
The water-resistant paper of the present embodiment is excellent in water resistance and heat-sealing properties, and is therefore excellent in moldability.
以下に実施例と比較例を挙げて本実施形態の特徴をさらに具体的に説明する。以下の実施例に示す材料、使用量、割合、処理内容、処理手順等は、本発明の趣旨を逸脱しない限り適宜変更することができる。従って、本発明の範囲は以下に示す具体例により限定的に解釈されるべきものではない。なお、％は、特に断りのない限り、質量％を意味する。 The characteristics of the present embodiment will be described more specifically below with reference to examples and comparative examples. The materials, amounts used, proportions, treatment details, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed to be limited by the specific examples shown below. In addition, % means the mass % unless there is particular notice.
実施例および比較例で使用した原材料は、以下の通りである。
［樹脂成分］
・エチレン－メタクリル酸共重合体アイオノマー：エチレン－メタクリル酸共重合物の金属塩の水系分散液、商品名「ケミパールＳ－３００」、三井化学株式会社製、固形分濃度３５．０質量％
・エチレン－アクリル酸共重合体アイオノマー：エチレン－アクリル酸共重合体アンモニウム塩の水系分散液、商品名「ザイクセンＡＣ」、住友精化株式会社製、固形分濃度２９．３質量％、アクリル酸の共重合比率２１．１質量％
Raw materials used in Examples and Comparative Examples are as follows.
[Resin component]
・ Ethylene-methacrylic acid copolymer ionomer: Aqueous dispersion of metal salt of ethylene-methacrylic acid copolymer, trade name “Chemipearl S-300”, manufactured by Mitsui Chemicals, Inc., solid content concentration 35.0% by mass
・ Ethylene-acrylic acid copolymer ionomer: Aqueous dispersion of ethylene-acrylic acid copolymer ammonium salt, trade name “Zaixen AC”, manufactured by Sumitomo Seika Co., Ltd., solid content concentration 29.3% by mass, acrylic acid Copolymerization ratio 21.1% by mass
［粒子成分（有機粒子、無機粒子（顔料））］
・カオリン／ＳＢＲ＝４／６、商品名「ＶＢ２１６０」、カオリンの粒径＝０．１～４μｍ、マイケルマンジャパン合同会社製
・高密度ＰＥ（ＨＤＰＥ）、商品名「ＭＥ６１３３５Ｐ（ＭＩＣＨＥＭ ＥＭＵＬＳＩＯＮ ６１３３５Ｐ）」、マイケルマンジャパン合同会社製、粒径３０～６０ｎｍ
・低分子量ＰＥ＋変性ＰＯ（変性ポリオレフィン、低分子量ＰＯ）、商品名「ケミパールＷ３１０」、三井化学株式会社製、粒径９．５μｍ
・エンジニアードカオリン、商品名「バリサーフＨＸ」、株式会社イメリスミネラルズ・ジャパン製、平均粒径２．０μｍ、アスペクト比１００
［その他］
・消泡剤：商品名「ビスマーＫＳ３８－Ｅ」、株式会社日新化学研究所製
[Particle component (organic particles, inorganic particles (pigment))]
・ Kaolin / SBR = 4/6, product name “VB2160”, kaolin particle size = 0.1 to 4 μm, manufactured by Michael Mann Japan LLC ・ High density PE (HDPE), product name “ME61335P (MICEM EMULSION 61335P)” , manufactured by Michael Mann Japan LLC, particle size 30 to 60 nm
・ Low molecular weight PE + modified PO (modified polyolefin, low molecular weight PO), trade name “Chemipearl W310”, manufactured by Mitsui Chemicals, Inc., particle size 9.5 μm
・Engineered kaolin, trade name “Balisurf HX”, manufactured by Imerys Minerals Japan Co., Ltd., average particle size 2.0 μm, aspect ratio 100
[others]
・ Antifoaming agent: trade name "Bismer KS38-E", manufactured by Nisshin Chemical Laboratory Co., Ltd.
［実施例１］
（ａ）顔料層塗工液Ａの作製
カオリン／ＳＢＲ＝４／６のＶＢ２１６０に、消泡剤を配合して、固形分中のＶＢ２１６０の含有量が９８．９質量％、消泡剤の含有量が１．１質量％であり、固形分濃度４０．０質量％の顔料層塗工液Ａ（塗工液Ａ）を調製した。
（ｂ）塗工液Ｂの作製
エチレン－メタクリル酸共重合体アイオノマーに、ＨＤＰＥと消泡剤を配合して、固形分中のエチレン－メタクリル酸共重合体アイオノマーの含有量が７５．８質量％、ＨＤＰＥの含有量が２２．７質量％であり、消泡剤の含有量が１．５質量％であり、固形分濃度３０質量％の塗工液Ｂを調製した。
[Example 1]
(a) Preparation of Pigment Layer Coating Solution A VB2160 with kaolin/SBR = 4/6 was blended with an antifoaming agent so that the content of VB2160 in the solid content was 98.9% by mass, and the content of the antifoaming agent was 98.9% by mass. A pigment layer coating liquid A (coating liquid A) having a solid content concentration of 40.0 mass % was prepared.
(b) Preparation of coating liquid B HDPE and an antifoaming agent were blended with an ethylene-methacrylic acid copolymer ionomer, and the content of the ethylene-methacrylic acid copolymer ionomer in the solid content was 75.8% by mass. , HDPE content of 22.7% by mass, antifoaming agent content of 1.5% by mass, and solid content concentration of 30% by mass.
＜耐水性紙の作製＞
坪量が２２４ｇ／ｍ２、紙厚が２６８μｍの紙基材の片面（表面）に、上記塗工液Ａを、塗工量（固形分）が２．５ｇ／ｍ２となるように、エアナイフコーターを用いて塗工して、乾燥させ、顔料塗工層（以下、表顔料層と称する）を形成したのち、同じ面に、塗工液Ｂを、塗工量（固形分）が２．５ｇ／ｍ２となるように、グラビアコーターを用いて塗工して、乾燥させ、下塗り耐水性層（以下、表１層目と称する、膜厚約２．５μｍ）を形成したのち、同じ面に、再度塗工液Ｂを、塗工量（固形分）が２．５ｇ／ｍ２となるように、グラビアコーターを用いて塗工して、乾燥させ、下塗り耐水性層（以下、表２層目と称する、膜厚約２．５μｍ）を形成した。同じ面に、上記塗工液Ｂを、塗工量（固形分）が５．０ｇ／ｍ２となるように、エアナイフコーターを用いて塗工して、乾燥させ、耐水性層（以下、表３層目と称する、膜厚約５．０μｍ）を形成し、１層の顔料塗工層と、２層の下塗り耐水性層と、１層の耐水性層をこの順で紙基材上に形成させた。
<Preparation of water-resistant paper>
On one side (surface) of a paper base material having a basis weight of 224 g/m 2 and a paper thickness of 268 μm, the above coating liquid A was applied to a coating amount (solid content) of 2.5 g/m 2 with an air knife. After coating with a coater and drying to form a pigment coating layer (hereinafter referred to as a surface pigment layer), the same surface was coated with Coating Solution B in a coating amount (solid content) of 2. It is coated using a gravure coater so as to be 5 g / m 2 , dried, and a water-resistant undercoat layer (hereinafter referred to as the first layer in the table, thickness of about 2.5 μm) is formed. After that, the same surface Then, the coating liquid B was applied again using a gravure coater so that the coating amount (solid content) was 2.5 g / m 2 , dried, and the undercoat water-resistant layer (hereinafter, Table 2 A film thickness of about 2.5 μm) was formed. On the same surface, the above coating solution B is applied using an air knife coater so that the coating amount (solid content) is 5.0 g / m 2 , dried, and a water resistant layer (hereinafter referred to as the surface A third layer (thickness of about 5.0 μm) is formed, and one pigment coating layer, two water-resistant undercoat layers, and one water-resistant layer are placed in this order on the paper base. formed.
［実施例２］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
（ｃ）塗工液Ｃの作製
エチレン－メタクリル酸共重合体アイオノマーに、ＨＤＰＥと消泡剤を配合して、固形分中のエチレン－メタクリル酸共重合体アイオノマーの含有量が９４．３質量％、ＨＤＰＥの含有量が３．８質量％であり、消泡剤の含有量が１．９質量％であり、固形分濃度３０質量％の塗工液Ｃを調製した。
[Example 2]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(c) Preparation of coating liquid C Ethylene-methacrylic acid copolymer ionomer was blended with HDPE and an antifoaming agent so that the content of ethylene-methacrylic acid copolymer ionomer in the solid content was 94.3% by mass. , the content of HDPE was 3.8% by mass, the content of the antifoaming agent was 1.9% by mass, and a coating liquid C having a solid content concentration of 30% by mass was prepared.
＜耐水性紙の作製＞
塗工液Ｂを上記（ｃ）の塗工液Ｃに変更した以外は実施例１と同様にして、耐水性紙を作製した。
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 1, except that the coating liquid B was changed to the coating liquid C of the above (c).
［実施例３］
実施例１と同様に（ａ）顔料層塗工液Ａ、（ｂ）塗工液Ｂを作製した。
（ｄ）塗工液Ｄの作製
エチレン－メタクリル酸共重合体アイオノマーに、消泡剤を配合して、固形分中のエチレン－メタクリル酸共重合体アイオノマーの含有量が９８．０質量％、消泡剤の含有量が２．０質量％であり、固形分濃度３０質量％の塗工液Ｄを調製した。
[Example 3]
In the same manner as in Example 1, (a) pigment layer coating liquid A and (b) coating liquid B were prepared.
(d) Preparation of coating liquid D Ethylene-methacrylic acid copolymer ionomer is blended with an antifoaming agent so that the content of ethylene-methacrylic acid copolymer ionomer in the solid content is 98.0% by mass. A coating liquid D having a foaming agent content of 2.0% by mass and a solid concentration of 30% by mass was prepared.
＜耐水性紙の作製＞
坪量が２２４ｇ／ｍ２、紙厚が２６８μｍの紙基材の片面（表面）に、上記塗工液Ａを、塗工量（固形分）が２．５ｇ／ｍ２となるように、エアナイフコーターを用いて塗工して、乾燥させ、顔料塗工層（以下、表顔料層と称する）を形成したのち、同じ面に、塗工液Ｄを、塗工量（固形分）が２．５ｇ／ｍ２となるように、グラビアコーターを用いて塗工して、乾燥させ、下塗り耐水性層（以下、表１層目と称する、膜厚約２．５μｍ）を形成したのち、同じ面に、再度塗工液Ｄを、塗工量（固形分）が２．５ｇ／ｍ２となるように、グラビアコーターを用いて塗工して、乾燥させ、下塗り耐水性層（以下、表２層目と称する、膜厚約２．５μｍ）を形成した。同じ面に、上記塗工液Ｂを、塗工量（固形分）が５．０ｇ／ｍ２となるように、エアナイフコーターを用いて塗工して、乾燥させ、耐水性層（以下、表３層目と称する、膜厚約５．０μｍ）を形成し、１層の顔料塗工層と、２層の下塗り耐水性層と、１層の耐水性層とをこの順で基材上に形成させた。
<Preparation of water-resistant paper>
On one side (surface) of a paper base material having a basis weight of 224 g/m 2 and a paper thickness of 268 μm, the above coating liquid A was applied to a coating amount (solid content) of 2.5 g/m 2 with an air knife. After coating with a coater and drying to form a pigment coating layer (hereinafter referred to as a surface pigment layer), the same surface was coated with coating liquid D in a coating amount (solid content) of 2. It is coated using a gravure coater so as to be 5 g / m 2 , dried, and a water-resistant undercoat layer (hereinafter referred to as the first layer in the table, thickness of about 2.5 μm) is formed. After that, the same surface Then, the coating liquid D is applied again using a gravure coater so that the coating amount (solid content) is 2.5 g / m 2 , dried, and the undercoat water-resistant layer (hereinafter, Table 2 A film thickness of about 2.5 μm) was formed. On the same surface, the above coating solution B is applied using an air knife coater so that the coating amount (solid content) is 5.0 g / m 2 , dried, and a water resistant layer (hereinafter referred to as the surface A third layer (thickness of about 5.0 μm) is formed, and one pigment coating layer, two water-resistant undercoat layers, and one water-resistant layer are placed in this order on the substrate. formed.
［実施例４］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
実施例２と同様に（ｃ）塗工液Ｃを作製した。
実施例３と同様に（ｄ）塗工液Ｄを作製した。
＜耐水性紙の作製＞
塗工液Ｂを上記（ｃ）の塗工液Ｃに変更した以外は実施例３と同様にして、耐水性紙を作製した。
[Example 4]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(c) Coating Liquid C was prepared in the same manner as in Example 2.
(d) Coating Liquid D was prepared in the same manner as in Example 3.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 3, except that the coating liquid B was changed to the coating liquid C of the above (c).
［実施例５］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
（ｅ）塗工液Ｅの作製
エチレン－メタクリル酸共重合体アイオノマーに、低分子量ＰＥと消泡剤を配合して、固形分中のエチレン－メタクリル酸共重合体アイオノマーの含有量が９４．３質量％、低分子量ＰＥの含有量が３．８質量％であり、消泡剤の含有量が１．９質量％であり、固形分濃度３０質量％の塗工液Ｅを調製した。
[Example 5]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(e) Preparation of coating liquid E Ethylene-methacrylic acid copolymer ionomer was blended with low molecular weight PE and an antifoaming agent, and the content of ethylene-methacrylic acid copolymer ionomer in solid content was 94.3. %, the content of low-molecular-weight PE was 3.8% by mass, the content of defoaming agent was 1.9% by mass, and a coating liquid E was prepared having a solid content concentration of 30% by mass.
＜耐水性紙の作製＞
塗工液Ｂを上記（ｅ）の塗工液Ｅに変更した以外は実施例１と同様にして、耐水性紙を作製した。
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 1, except that the coating liquid B was changed to the coating liquid E of the above (e).
［実施例６］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
（ｆ）塗工液Ｆの作製
エチレン－メタクリル酸共重合体アイオノマーに、低分子量ＰＥと消泡剤を配合して、固形分中のエチレン－メタクリル酸共重合体アイオノマーの含有量が９６．２質量％、低分子量ＰＥの含有量が１．９質量％であり、消泡剤の含有量が１．９質量％であり、固形分濃度３０質量％の塗工液Ｆを調製した。
[Example 6]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(f) Preparation of coating liquid F Ethylene-methacrylic acid copolymer ionomer was blended with low molecular weight PE and an antifoaming agent, and the content of ethylene-methacrylic acid copolymer ionomer in solid content was 96.2. % by mass, a low molecular weight PE content of 1.9 mass %, an antifoaming agent content of 1.9 mass %, and a solid content concentration of 30 mass %.
＜耐水性紙の作製＞
塗工液Ｂを上記（ｆ）の塗工液Ｆに変更した以外は実施例１と同様にして、耐水性紙を作製した。
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 1, except that the coating liquid B was changed to the coating liquid F of the above (f).
［実施例７］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
実施例３と同様に（ｄ）塗工液Ｄを作製した。
実施例５と同様に（ｅ）塗工液Ｅを作製した。
＜耐水性紙の作製＞
塗工液Ｂを上記（ｅ）の塗工液Ｅに変更した以外は実施例３と同様にして、耐水性紙を作製した。
[Example 7]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(d) Coating Liquid D was prepared in the same manner as in Example 3.
(e) Coating liquid E was prepared in the same manner as in Example 5.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 3, except that the coating liquid B was changed to the coating liquid E of (e) above.
［実施例８］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
実施例３と同様に（ｄ）塗工液Ｄを作製した。
実施例６と同様に（ｆ）塗工液Ｆを作製した。
＜耐水性紙の作製＞
塗工液Ｂを上記（ｆ）の塗工液Ｆに変更した以外は実施例３と同様にして、耐水性紙を作製した。
[Example 8]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(d) Coating Liquid D was prepared in the same manner as in Example 3.
(f) Coating Liquid F was prepared in the same manner as in Example 6.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 3, except that the coating liquid B was changed to the coating liquid F of the above (f).
［実施例９］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
（ｋ）塗工液Ｋの作製
エチレン－メタクリル酸共重合体アイオノマーに、消泡剤を配合して、固形分中のエチレン－メタクリル酸共重合体アイオノマーの含有量が９８．９質量％、消泡剤の含有量が１．１質量％であり、固形分濃度３０質量％の塗工液Ｋを調製した。
（ｌ）塗工液Ｌの作製
エチレン－メタクリル酸共重合体アイオノマーに、低分子量ＰＥと消泡剤を配合して、固形分中のエチレン－メタクリル酸共重合体アイオノマーの含有量が９５．２質量％、低分子量ＰＥの含有量が３．８質量％であり、消泡剤の含有量が１．０質量％であり、固形分濃度３０質量％の塗工液Ｌを調製した。
＜耐水性紙の作製＞
塗工液Ｄを上記（ｋ）の塗工液Ｋに、塗工液Ｅを上記（ｌ）の塗工液Ｌに、変更した以外は実施例７と同様にして、耐水性紙を作製した。
[Example 9]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(k) Preparation of coating liquid K Ethylene-methacrylic acid copolymer ionomer is blended with an antifoaming agent so that the content of ethylene-methacrylic acid copolymer ionomer in the solid content is 98.9% by mass. A coating liquid K having a foaming agent content of 1.1% by mass and a solid concentration of 30% by mass was prepared.
(l) Preparation of coating liquid L Ethylene-methacrylic acid copolymer ionomer was blended with low molecular weight PE and an antifoaming agent so that the content of ethylene-methacrylic acid copolymer ionomer in the solid content was 95.2. % by mass, the content of low-molecular-weight PE was 3.8% by mass, the content of defoaming agent was 1.0% by mass, and a coating liquid L with a solid content concentration of 30% by mass was prepared.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 7, except that the coating solution D was changed to the coating solution K of the above (k), and the coating solution E was changed to the coating solution L of the above (l). .
［実施例１０］
坪量が２４６ｇ／ｍ２、紙厚が２７４μｍの紙基材に変更した以外は、実施例９と同様にして、耐水性紙を作製した。
[Example 10]
Water-resistant paper was produced in the same manner as in Example 9, except that the basis weight was changed to 246 g/m 2 and the paper thickness was changed to 274 μm.
［実施例１１］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
実施例９と同様に（ｋ）塗工液Ｋを作製した。
（ｍ）塗工液Ｍの作製
エチレン－メタクリル酸共重合体アイオノマーに、低分子量ＰＥと消泡剤を配合して、固形分中のエチレン－メタクリル酸共重合体アイオノマーの含有量が９１．７質量％、低分子量ＰＥの含有量が７．３質量％であり、消泡剤の含有量が１．０質量％であり、固形分濃度３０質量％の塗工液Ｍを調製した。
＜耐水性紙の作製＞
塗工液Ｌを上記（ｍ）の塗工液Ｍに変更した以外は実施例９と同様にして、耐水性紙を作製した。
[Example 11]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(k) Coating Liquid K was prepared in the same manner as in Example 9.
(m) Preparation of coating liquid M Ethylene-methacrylic acid copolymer ionomer was blended with low-molecular-weight PE and an antifoaming agent so that the content of ethylene-methacrylic acid copolymer ionomer in the solid content was 91.7. % by mass, the content of low-molecular-weight PE was 7.3% by mass, the content of defoaming agent was 1.0% by mass, and a coating liquid M with a solid content concentration of 30% by mass was prepared.
<Preparation of water-resistant paper>
Water-resistant paper was produced in the same manner as in Example 9, except that the coating liquid L was changed to the coating liquid M of the above (m).
［実施例１２］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
実施例９と同様に（ｋ）塗工液Ｋを作製した。
（ｎ）塗工液Ｎの作製
エチレン－メタクリル酸共重合体アイオノマーに、低分子量ＰＥと消泡剤を配合して、固形分中のエチレン－メタクリル酸共重合体アイオノマーの含有量が８２．６質量％、低分子量ＰＥの含有量が１６．５質量％であり、消泡剤の含有量が０．９質量％であり、固形分濃度３０質量％の塗工液Ｎを調製した。
＜耐水性紙の作製＞
塗工液Ｌを上記（ｎ）の塗工液Ｎに変更した以外は実施例９と同様にして、耐水性紙を作製した。
[Example 12]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(k) Coating Liquid K was prepared in the same manner as in Example 9.
(n) Preparation of coating liquid N Ethylene-methacrylic acid copolymer ionomer was blended with low-molecular-weight PE and an antifoaming agent so that the content of ethylene-methacrylic acid copolymer ionomer in the solid content was 82.6. % by mass, the content of low-molecular-weight PE was 16.5% by mass, the content of defoaming agent was 0.9% by mass, and the solid content concentration was 30% by mass.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 9, except that the coating liquid L was changed to the coating liquid N of (n) above.
［実施例１３］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
実施例３と同様に（ｄ）塗工液Ｄを作製した。
実施例１と同様に（ｂ）塗工液Ｂを作製した。
＜耐水性紙の作製＞
裏面に、塗工液Ｂを、塗工量（固形分）が２．５ｇ／ｍ２となるように、グラビアコーターを用いて塗工して、乾燥させ、下塗り耐水性層（以下、裏１層目と称する、膜厚約２．５μｍ）を形成したのち、同じ面に、再度塗工液Ｂを、塗工量（固形分）が２．５ｇ／ｍ２となるように、グラビアコーターを用いて塗工して、乾燥させ、下塗り耐水性層（以下、裏２層目と称する、膜厚約２．５μｍ）を形成した。同じ面に、上記塗工液Ｂを、塗工量（固形分）が５．０ｇ／ｍ２となるように、エアナイフコーターを用いて塗工して、乾燥させ、耐水性層（以下、裏３層目と称する、膜厚約５．０μｍ）を形成した。
また、その反対面（表面）に、塗工液Ｂを上記（ｄ）の塗工液Ｄに変更した以外は実施例１と同様にして、表面に耐水性を有する層を形成した。片面（裏面）に２層の下塗り耐水性層および１層の耐水性層、および反対面（表面）に１層の顔料塗工層と３層の耐水性を有する層を形成させた。
[Example 13]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(d) Coating Liquid D was prepared in the same manner as in Example 3.
(b) Coating Liquid B was prepared in the same manner as in Example 1.
<Preparation of water-resistant paper>
Coating liquid B is applied to the back surface using a gravure coater so that the coating amount (solid content) is 2.5 g / m 2 and dried to form a water-resistant undercoat layer (hereinafter referred to as back 1 After forming a film thickness of about 2.5 μm, which is called a second layer, the gravure coater is applied to the same surface again so that the coating amount (solid content) is 2.5 g / m 2 . and dried to form a water-resistant undercoat layer (hereinafter referred to as the second back layer, with a film thickness of about 2.5 μm). On the same surface, the coating liquid B is applied using an air knife coater so that the coating amount (solid content) is 5.0 g / m 2 , dried, and a water resistant layer (hereinafter referred to as the back A film thickness of about 5.0 μm, which is called a third layer, was formed.
On the opposite side (surface), a layer having water resistance was formed on the surface in the same manner as in Example 1, except that the coating liquid B was changed to the coating liquid D of the above (d). Two water-resistant undercoat layers and one water-resistant layer were formed on one side (back side), and one pigment coating layer and three water-resistant layers were formed on the opposite side (front side).
［実施例１４］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
実施例３と同様に（ｄ）塗工液Ｄを作製した。
実施例２と同様に（ｃ）塗工液Ｃを作製した。
＜耐水性紙の作製＞
塗工液Ｂを上記（ｃ）の塗工液Ｃに変更した以外は実施例１３と同様にして、耐水性紙を作製した。
[Example 14]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(d) Coating Liquid D was prepared in the same manner as in Example 3.
(c) Coating Liquid C was prepared in the same manner as in Example 2.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 13, except that the coating liquid B was changed to the coating liquid C of the above (c).
［実施例１５］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
実施例３と同様に（ｄ）塗工液Ｄを作製した。
実施例２と同様に（ｂ）塗工液Ｂを作製した。
＜耐水性紙の作製＞
裏面に、塗工液Ｄを、塗工量（固形分）が２．５ｇ／ｍ２となるように、グラビアコーターを用いて塗工して、乾燥させ、下塗り耐水性層（以下、裏１層目と称する、膜厚約２．５μｍ）を形成したのち、同じ面に、再度塗工液Ｄを、塗工量（固形分）が２．５ｇ／ｍ２となるように、グラビアコーターを用いて塗工して、乾燥させ、下塗り耐水性層（以下、裏２層目と称する、膜厚約２．５μｍ）を形成した。同じ面に、上記塗工液Ｂを、塗工量（固形分）が５．０ｇ／ｍ２となるように、エアナイフコーターを用いて塗工して、乾燥させ、耐水性層（以下、裏３層目と称する、膜厚約５．０μｍ）を形成した。
また、その反対面（表面）に、塗工液Ｂを上記（ｄ）の塗工液Ｄに変更した以外は実施例１と同様にして、表面に耐水性を有する層を形成した。片面（裏面）に２層の下塗り耐水性層および１層の耐水性層、反対面（表面）に１層の顔料塗工層と３層の耐水性を有する層を形成させた。
[Example 15]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(d) Coating Liquid D was prepared in the same manner as in Example 3.
(b) Coating liquid B was prepared in the same manner as in Example 2.
<Preparation of water-resistant paper>
Coating liquid D is applied to the back surface using a gravure coater so that the coating amount (solid content) is 2.5 g / m 2 and dried to form a water-resistant undercoat layer (hereinafter referred to as back 1 After forming a film thickness of about 2.5 μm, which is called a second layer, the gravure coater is applied to the same surface again so that the coating amount (solid content) is 2.5 g / m 2 . and dried to form a water-resistant undercoat layer (hereinafter referred to as the second back layer, with a film thickness of about 2.5 μm). On the same surface, the coating liquid B is applied using an air knife coater so that the coating amount (solid content) is 5.0 g / m 2 , dried, and a water resistant layer (hereinafter referred to as the back A film thickness of about 5.0 μm, which is called a third layer, was formed.
On the opposite side (surface), a layer having water resistance was formed on the surface in the same manner as in Example 1, except that the coating liquid B was changed to the coating liquid D of the above (d). Two water-resistant undercoat layers and one water-resistant layer were formed on one side (back side), and one pigment coating layer and three water-resistant layers were formed on the opposite side (front side).
［実施例１６］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
実施例３と同様に（ｄ）塗工液Ｄを作製した。
実施例２と同様に（ｃ）塗工液Ｃを作製した。
＜耐水性紙の作製＞
塗工液Ｂを上記（ｃ）の塗工液Ｃに変更した以外は実施例１５と同様にして、耐水性紙を作製した。
[Example 16]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(d) Coating Liquid D was prepared in the same manner as in Example 3.
(c) Coating Liquid C was prepared in the same manner as in Example 2.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 15, except that the coating liquid B was changed to the coating liquid C of the above (c).
［実施例１７］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
実施例３と同様に（ｄ）塗工液Ｄを作製した。
実施例５と同様に（ｅ）塗工液Ｅを作製した。
＜耐水性紙の作製＞
塗工液Ｂを上記（ｅ）の塗工液Ｅに変更した以外は実施例１３と同様にして、耐水性紙を作製した。
[Example 17]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(d) Coating Liquid D was prepared in the same manner as in Example 3.
(e) Coating liquid E was prepared in the same manner as in Example 5.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 13, except that the coating liquid B was changed to the coating liquid E of the above (e).
［実施例１８］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
実施例３と同様に（ｄ）塗工液Ｄを作製した。
実施例６と同様に（ｆ）塗工液Ｆを作製した。
＜耐水性紙の作製＞
塗工液Ｂを上記（ｆ）の塗工液Ｆに変更した以外は実施例１３と同様にして、耐水性紙を作製した。
[Example 18]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(d) Coating Liquid D was prepared in the same manner as in Example 3.
(f) Coating Liquid F was prepared in the same manner as in Example 6.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 13, except that the coating liquid B was changed to the coating liquid F of the above (f).
［実施例１９］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
実施例３と同様に（ｄ）塗工液Ｄを作製した。
実施例５と同様に（ｅ）塗工液Ｅを作製した。
＜耐水性紙の作製＞
塗工液Ｂを上記（ｅ）の塗工液Ｅに変更した以外は実施例１５と同様にして、耐水性紙を作製した。
[Example 19]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(d) Coating Liquid D was prepared in the same manner as in Example 3.
(e) Coating liquid E was prepared in the same manner as in Example 5.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 15, except that the coating liquid B was changed to the coating liquid E of the above (e).
［実施例２０］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
実施例３と同様に（ｄ）塗工液Ｄを作製した。
実施例６と同様に（ｆ）塗工液Ｆを作製した。
＜耐水性紙の作製＞
塗工液Ｂを上記（ｆ）の塗工液Ｆに変更した以外は実施例１５と同様にして、耐水性紙を作製した。
[Example 20]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(d) Coating Liquid D was prepared in the same manner as in Example 3.
(f) Coating Liquid F was prepared in the same manner as in Example 6.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 15, except that the coating liquid B was changed to the coating liquid F of the above (f).
［実施例２１］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
実施例９と同様に（ｋ）塗工液Ｋを作製した。
実施例９と同様に（ｌ）塗工液Ｌを作製した。
＜耐水性紙の作製＞
塗工液Ｄを上記（ｋ）の塗工液Ｋに、塗工液Ｂを上記（ｌ）の塗工液Ｌに、変更した以外は実施例１５と同様にして、耐水性紙を作製した。
[Example 21]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(k) Coating Liquid K was prepared in the same manner as in Example 9.
(1) Coating liquid L was prepared in the same manner as in Example 9.
<Preparation of water-resistant paper>
A water-resistant paper was produced in the same manner as in Example 15, except that the coating solution D was changed to the coating solution K of the above (k), and the coating solution B was changed to the coating solution L of the above (l). .
［実施例２２］
坪量が２４６ｇ／ｍ２、紙厚が２７４μｍの紙基材に変更した以外は、実施例２１と同様にして、耐水性紙を作製した。
[Example 22]
Water-resistant paper was produced in the same manner as in Example 21, except that the basis weight was changed to 246 g/m 2 and the paper thickness was changed to 274 μm.
［実施例２３］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
実施例９と同様に（ｋ）塗工液Ｋを作製した。
実施例１１と同様に（ｍ）塗工液Ｍを作製した。
＜耐水性紙の作製＞
塗工液Ｌを上記（ｍ）の塗工液Ｍに変更した以外は実施例２１と同様にして、耐水性紙を作製した。
[Example 23]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(k) Coating Liquid K was prepared in the same manner as in Example 9.
(m) Coating Liquid M was prepared in the same manner as in Example 11.
<Preparation of water-resistant paper>
A water-resistant paper was produced in the same manner as in Example 21, except that the coating liquid L was changed to the coating liquid M of the above (m).
［実施例２４］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
実施例９と同様に（ｋ）塗工液Ｋを作製した。
実施例１２と同様に（ｎ）塗工液Ｎを作製した。
＜耐水性紙の作製＞
塗工液Ｌを上記（ｎ）の塗工液Ｎに変更した以外は実施例２１と同様にして、耐水性紙を作製した。
[Example 24]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(k) Coating Liquid K was prepared in the same manner as in Example 9.
(n) Coating Liquid N was prepared in the same manner as in Example 12.
<Preparation of water-resistant paper>
Water-resistant paper was produced in the same manner as in Example 21, except that the coating liquid L was changed to the coating liquid N of (n) above.
［実施例２５］
（ｏ）塗工液Ｏの作製
エチレン－メタクリル酸共重合体アイオノマーに、ＨＤＰＥと消泡剤を配合して、固形分中のエチレン－メタクリル酸共重合体アイオノマーの含有量が７６．３質量％、ＨＤＰＥの含有量が２２．９質量％であり、消泡剤の含有量が０．８質量％であり、固形分濃度３０質量％の塗工液Ｏを調製した。
＜耐水性紙の作製＞
坪量が２２４ｇ／ｍ２、紙厚が２６８μｍの紙基材の片面（表面）に、上記塗工液Ｏを、塗工量（固形分）が２．５ｇ／ｍ２となるように、グラビアコーターを用いて塗工して、乾燥させ、下塗り耐水性層（以下、表１層目と称する、膜厚約２．５μｍ）を形成したのち、同じ面に、再度塗工液Ｏを、塗工量（固形分）が２．５ｇ／ｍ２となるように、グラビアコーターを用いて塗工して、乾燥させ、下塗り耐水性層（以下、表２層目と称する、膜厚約２．５μｍ）を形成した。同じ面に、上記塗工液Ｏを、塗工量（固形分）が５．０ｇ／ｍ２となるように、エアナイフコーターを用いて塗工して、乾燥させ、耐水性層（以下、表３層目と称する、膜厚約５．０μｍ）を形成し、２層の下塗り耐水性層と、１層の耐水性層をこの順で紙基材上に形成させた。
[Example 25]
(O) Preparation of coating liquid O HDPE and an antifoaming agent were blended with an ethylene-methacrylic acid copolymer ionomer, and the content of the ethylene-methacrylic acid copolymer ionomer in the solid content was 76.3% by mass. , the content of HDPE was 22.9% by mass, the content of the antifoaming agent was 0.8% by mass, and the solid content concentration was 30% by mass.
<Preparation of water-resistant paper>
On one side (surface) of a paper substrate having a basis weight of 224 g/m 2 and a paper thickness of 268 μm, the coating liquid O is applied to a gravure coating amount (solid content) of 2.5 g/m 2 . After coating with a coater and drying to form a water-resistant undercoat layer (hereinafter referred to as the first layer in the table, with a thickness of about 2.5 μm), the coating liquid O is applied again on the same surface. It was applied using a gravure coater so that the work weight (solid content) was 2.5 g/m 2 , dried, and the undercoat water-resistant layer (hereinafter referred to as the second layer in the table, the thickness of which was about 2.5 g/m 2 ). 5 μm). On the same surface, the above coating liquid O is applied using an air knife coater so that the coating amount (solid content) is 5.0 g / m 2 , dried, and a water resistant layer (hereinafter referred to as the surface A film thickness of about 5.0 μm, which is referred to as a third layer, was formed, and two water-resistant undercoat layers and one water-resistant layer were formed in this order on the paper substrate.
［実施例２６］
（ｐ）塗工液Ｐの作製
エチレン－メタクリル酸共重合体アイオノマーに、ＨＤＰＥと消泡剤を配合して、固形分中のエチレン－メタクリル酸共重合体アイオノマーの含有量が９５．２質量％、ＨＤＰＥの含有量が３．８質量％であり、消泡剤の含有量が１．０質量％であり、固形分濃度３０質量％の塗工液Ｐを調製した。
＜耐水性紙の作製＞
塗工液Ｏを上記（ｐ）の塗工液Ｐに変更した以外は実施例２５と同様にして、耐水性紙を作製した。
[Example 26]
(p) Preparation of coating liquid P Ethylene-methacrylic acid copolymer ionomer was blended with HDPE and an antifoaming agent so that the content of ethylene-methacrylic acid copolymer ionomer in the solid content was 95.2% by mass. , a HDPE content of 3.8% by mass, an antifoaming agent content of 1.0% by mass, and a solid content concentration of 30% by mass.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 25, except that the coating liquid O was changed to the coating liquid P of (p) above.
［実施例２７］
実施例９と同様に（ｋ）塗工液Ｋを作製した。
実施例２５と同様に（ｏ）塗工液Ｏを作製した。
＜耐水性紙の作製＞
坪量が２２４ｇ／ｍ２、紙厚が２６８μｍの紙基材の片面（表面）に、塗工液Ｋを、塗工量（固形分）が２．５ｇ／ｍ２となるように、グラビアコーターを用いて塗工して、乾燥させ、下塗り耐水性層（以下、表１層目と称する、膜厚約２．５μｍ）を形成したのち、同じ面に、再度塗工液Ｋを、塗工量（固形分）が２．５ｇ／ｍ２となるように、グラビアコーターを用いて塗工して、乾燥させ、下塗り耐水性層（以下、表２層目と称する、膜厚約２．５μｍ）を形成した。同じ面に、上記塗工液Ｏを、塗工量（固形分）が５．０ｇ／ｍ２となるように、エアナイフコーターを用いて塗工して、乾燥させ、耐水性層（以下、表３層目と称する、膜厚約５．０μｍ）を形成し、２層の下塗り耐水性層と、１層の耐水性層とをこの順で基材上に形成させた。
[Example 27]
(k) Coating Liquid K was prepared in the same manner as in Example 9.
(o) Coating liquid O was prepared in the same manner as in Example 25.
<Preparation of water-resistant paper>
A gravure coater was applied to one side (surface) of a paper substrate having a basis weight of 224 g/m 2 and a paper thickness of 268 μm so that the coating amount (solid content) was 2.5 g/m 2 . and dried to form a water-resistant undercoat layer (hereinafter referred to as the first layer in the table, with a thickness of about 2.5 μm), and then the coating liquid K is applied again on the same surface. It is coated using a gravure coater so that the amount (solid content) is 2.5 g / m 2 , dried, and a water-resistant undercoat layer (hereinafter referred to as the second layer in the table, with a thickness of about 2.5 μm ) was formed. On the same surface, the above coating liquid O is applied using an air knife coater so that the coating amount (solid content) is 5.0 g / m 2 , dried, and a water resistant layer (hereinafter referred to as the surface A film thickness of about 5.0 μm, which is referred to as a third layer, was formed, and two layers of the undercoat water-resistant layer and one layer of the water-resistant layer were formed on the substrate in this order.
［実施例２８］
実施例９と同様に（ｋ）塗工液Ｋを作製した。
実施例２６と同様に（ｐ）塗工液Ｐを作製した。
＜耐水性紙の作製＞
塗工液Ｏを上記（ｐ）の塗工液Ｐに変更した以外は実施例２７と同様にして、耐水性紙を作製した。
[Example 28]
(k) Coating Liquid K was prepared in the same manner as in Example 9.
(p) Coating liquid P was prepared in the same manner as in Example 26.
<Preparation of water-resistant paper>
A water-resistant paper was produced in the same manner as in Example 27, except that the coating liquid O was changed to the coating liquid P of the above (p).
［実施例２９］
実施例９と同様に（ｌ）塗工液Ｌを作製した。
＜耐水性紙の作製＞
塗工液Ｏを上記（ｌ）の塗工液Ｌに変更した以外は実施例２５と同様にして、耐水性紙を作製した。
[Example 29]
(1) Coating liquid L was prepared in the same manner as in Example 9.
<Preparation of water-resistant paper>
A water-resistant paper was produced in the same manner as in Example 25, except that the coating liquid O was changed to the coating liquid L of (l) above.
［実施例３０］
（ｑ）塗工液Ｑの作製
エチレン－メタクリル酸共重合体アイオノマーに、低分子量ＰＥと消泡剤を配合して、固形分中のエチレン－メタクリル酸共重合体アイオノマーの含有量が９７．０質量％、低分子量ＰＥの含有量が１．９質量％であり、消泡剤の含有量が１．１質量％であり、固形分濃度３０質量％の塗工液Ｐを調製した。
＜耐水性紙の作製＞
塗工液Ｏを上記（ｑ）の塗工液Ｑに変更した以外は実施例２５と同様にして、耐水性紙を作製した。
[Example 30]
(q) Preparation of coating liquid Q Ethylene-methacrylic acid copolymer ionomer was blended with low molecular weight PE and an antifoaming agent so that the content of ethylene-methacrylic acid copolymer ionomer in the solid content was 97.0. % by mass, the content of low-molecular-weight PE was 1.9% by mass, the content of defoaming agent was 1.1% by mass, and a coating liquid P with a solid content concentration of 30% by mass was prepared.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 25, except that the coating liquid O was changed to the coating liquid Q of the above (q).
［実施例３１］
実施例９と同様に（ｋ）塗工液Ｋを作製した。
実施例９と同様に（ｌ）塗工液Ｌを作製した。
＜耐水性紙の作製＞
塗工液Ｏを上記（ｌ）の塗工液Ｌに変更した以外は実施例２７と同様にして、耐水性紙を作製した。
[Example 31]
(k) Coating Liquid K was prepared in the same manner as in Example 9.
(1) Coating liquid L was prepared in the same manner as in Example 9.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 27, except that the coating liquid O was changed to the coating liquid L of (l) above.
［実施例３２］
実施例９と同様に（ｋ）塗工液Ｋを作製した。
実施例３０と同様に（ｑ）塗工液Ｑを作製した。
＜耐水性紙の作製＞
塗工液Ｏを上記（ｑ）の塗工液Ｑに変更した以外は実施例２７と同様にして、耐水性紙を作製した。
[Example 32]
(k) Coating Liquid K was prepared in the same manner as in Example 9.
(q) Coating liquid Q was prepared in the same manner as in Example 30.
<Preparation of water-resistant paper>
Water-resistant paper was produced in the same manner as in Example 27, except that the coating liquid O was changed to the coating liquid Q of the above (q).
［実施例３３］
実施例９と同様に（ｋ）塗工液Ｋを作製した。
実施例１１と同様に（ｍ）塗工液Ｍを作製した。
＜耐水性紙の作製＞
塗工液Ｏを上記（ｍ）の塗工液Ｍに変更した以外は実施例２７と同様にして、耐水性紙を作製した。
[Example 33]
(k) Coating Liquid K was prepared in the same manner as in Example 9.
(m) Coating Liquid M was prepared in the same manner as in Example 11.
<Preparation of water-resistant paper>
A water-resistant paper was produced in the same manner as in Example 27, except that the coating liquid O was changed to the coating liquid M of the above (m).
［実施例３４］
実施例９と同様に（ｋ）塗工液Ｋを作製した。
実施例１２と同様に（ｎ）塗工液Ｎを作製した。
＜耐水性紙の作製＞
塗工液Ｏを上記（ｎ）の塗工液Ｎに変更した以外は実施例２７と同様にして、耐水性紙を作製した。
[Example 34]
(k) Coating Liquid K was prepared in the same manner as in Example 9.
(n) Coating Liquid N was prepared in the same manner as in Example 12.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 27, except that the coating liquid O was changed to the coating liquid N of (n) above.
［実施例３５］
坪量が２４６ｇ／ｍ２、紙厚が２７４μｍの紙基材に変更した以外は、実施例３１と同様にして、耐水性紙を作製した。
[Example 35]
Water-resistant paper was produced in the same manner as in Example 31, except that the basis weight was changed to 246 g/m 2 and the paper thickness was changed to 274 μm.
［実施例３６］
実施例２５と同様に（ｏ）塗工液Ｏを作製した。
実施例９と同様に（ｋ）塗工液Ｋを作製した。
＜耐水性紙の作製＞
裏面に、塗工液Ｏを、塗工量（固形分）が２．５ｇ／ｍ２となるように、グラビアコーターを用いて塗工して、乾燥させ、下塗り耐水性層（以下、裏１層目と称する、膜厚約２．５μｍ）を形成したのち、同じ面に、再度塗工液Ｏを、塗工量（固形分）が２．５ｇ／ｍ２となるように、グラビアコーターを用いて塗工して、乾燥させ、下塗り耐水性層（以下、裏２層目と称する、膜厚約２．５μｍ）を形成した。同じ面に、上記塗工液Ｏを、塗工量（固形分）が５．０ｇ／ｍ２となるように、エアナイフコーターを用いて塗工して、乾燥させ、耐水性層（以下、裏３層目と称する、膜厚約５．０μｍ）を形成した。
また、その反対面（表面）に、塗工液Ｏを上記（ｋ）の塗工液Ｋに変更した以外は実施例２５と同様にして、表面に耐水性を有する層を形成した。片面（裏面）に２層の下塗り耐水性層および１層の耐水性層、および反対面（表面）に３層の耐水性を有する層を形成させた。
[Example 36]
(o) Coating liquid O was prepared in the same manner as in Example 25.
(k) Coating Liquid K was prepared in the same manner as in Example 9.
<Preparation of water-resistant paper>
Coating liquid O is applied to the back surface using a gravure coater so that the coating amount (solid content) is 2.5 g / m 2 and dried to form a water-resistant undercoat layer (hereinafter referred to as back 1 After forming a film thickness of about 2.5 μm, which is called a second layer, the gravure coater is applied to the same surface again so that the coating amount (solid content) is 2.5 g / m 2 . and dried to form a water-resistant undercoat layer (hereinafter referred to as the second back layer, with a film thickness of about 2.5 μm). On the same surface, the coating liquid O is applied using an air knife coater so that the coating amount (solid content) is 5.0 g / m 2 , dried, and a water resistant layer (hereinafter referred to as the back A film thickness of about 5.0 μm, which is called a third layer, was formed.
On the opposite side (surface), a water-resistant layer was formed on the surface in the same manner as in Example 25, except that the coating liquid O was changed to the coating liquid K of the above (k). Two water-resistant undercoat layers and one water-resistant layer were formed on one side (back side), and three water-resistant layers were formed on the opposite side (front side).
［実施例３７］
実施例２６と同様に（ｐ）塗工液Ｐを作製した。
＜耐水性紙の作製＞
塗工液Ｏを上記（ｐ）の塗工液Ｐに変更した以外は実施例３６と同様にして、耐水性紙を作製した。
[Example 37]
(p) Coating liquid P was prepared in the same manner as in Example 26.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 36, except that the coating liquid O was changed to the coating liquid P of (p) above.
［実施例３８］
実施例９と同様に（ｋ）塗工液Ｋを作製した。
実施例２５と同様に（ｏ）塗工液Ｏを作製した。
＜耐水性紙の作製＞
裏面に、塗工液Ｋを、塗工量（固形分）が２．５ｇ／ｍ２となるように、グラビアコーターを用いて塗工して、乾燥させ、下塗り耐水性層（以下、裏１層目と称する、膜厚約２．５μｍ）を形成したのち、同じ面に、再度塗工液Ｋを、塗工量（固形分）が２．５ｇ／ｍ２となるように、グラビアコーターを用いて塗工して、乾燥させ、下塗り耐水性層（以下、裏２層目と称する、膜厚約２．５μｍ）を形成した。同じ面に、上記塗工液Ｏを、塗工量（固形分）が５．０ｇ／ｍ２となるように、エアナイフコーターを用いて塗工して、乾燥させ、耐水性層（以下、裏３層目と称する、膜厚約５．０μｍ）を形成した。
また、その反対面（表面）に、塗工液Ｏを上記（ｋ）の塗工液Ｋに変更した以外は実施例２５と同様にして、表面に耐水性を有する層を形成した。片面（裏面）に２層の下塗り耐水性層および１層の耐水性層、反対面（表面）に３層の耐水性を有する層を形成させた。
[Example 38]
(k) Coating Liquid K was prepared in the same manner as in Example 9.
(o) Coating liquid O was prepared in the same manner as in Example 25.
<Preparation of water-resistant paper>
Coating liquid K is applied to the back surface using a gravure coater so that the coating amount (solid content) is 2.5 g / m 2 and dried to form a water-resistant undercoat layer (hereinafter referred to as back 1 After forming a film thickness of about 2.5 μm, which is called a second layer, the gravure coater is applied to the same surface again so that the coating amount (solid content) is 2.5 g / m 2 . and dried to form a water-resistant undercoat layer (hereinafter referred to as the second back layer, with a film thickness of about 2.5 μm). On the same surface, the coating liquid O is applied using an air knife coater so that the coating amount (solid content) is 5.0 g / m 2 , dried, and a water resistant layer (hereinafter referred to as the back A film thickness of about 5.0 μm, which is called a third layer, was formed.
On the opposite side (surface), a water-resistant layer was formed on the surface in the same manner as in Example 25, except that the coating liquid O was changed to the coating liquid K of the above (k). Two water-resistant undercoat layers and one water-resistant layer were formed on one side (back side), and three water-resistant layers were formed on the other side (front side).
［実施例３９］
実施例９と同様に（ｋ）塗工液Ｋを作製した。
実施例２６と同様に（ｐ）塗工液Ｐを作製した。
＜耐水性紙の作製＞
塗工液Ｏを上記（ｐ）の塗工液Ｐに変更した以外は実施例３８と同様にして、耐水性紙を作製した。
[Example 39]
(k) Coating Liquid K was prepared in the same manner as in Example 9.
(p) Coating liquid P was prepared in the same manner as in Example 26.
<Preparation of water-resistant paper>
Water-resistant paper was produced in the same manner as in Example 38, except that the coating liquid O was changed to the coating liquid P of the above (p).
［実施例４０］
実施例９と同様に（ｌ）塗工液Ｌを作製した。
＜耐水性紙の作製＞
塗工液Ｏを上記（ｌ）の塗工液Ｌに変更した以外は実施例３６と同様にして、耐水性紙を作製した。
[Example 40]
(1) Coating liquid L was prepared in the same manner as in Example 9.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 36, except that the coating liquid O was changed to the coating liquid L of (l) above.
［実施例４１］
実施例３０と同様に（ｑ）塗工液Ｑを作製した。
＜耐水性紙の作製＞
塗工液Ｏを上記（ｑ）の塗工液Ｑに変更した以外は実施例３６と同様にして、耐水性紙を作製した。
[Example 41]
(q) Coating liquid Q was prepared in the same manner as in Example 30.
<Preparation of water-resistant paper>
Water-resistant paper was produced in the same manner as in Example 36, except that the coating liquid O was changed to the coating liquid Q of the above (q).
［実施例４２］
実施例９と同様に（ｋ）塗工液Ｋを作製した。
実施例９と同様に（ｌ）塗工液Ｌを作製した。
＜耐水性紙の作製＞
塗工液Ｏを上記（ｌ）の塗工液Ｌに変更した以外は実施例３８と同様にして、耐水性紙を作製した。
[Example 42]
(k) Coating Liquid K was prepared in the same manner as in Example 9.
(1) Coating liquid L was prepared in the same manner as in Example 9.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 38, except that the coating liquid O was changed to the coating liquid L of (l) above.
［実施例４３］
実施例９と同様に（ｋ）塗工液Ｋを作製した。
実施例３０と同様に（ｑ）塗工液Ｑを作製した。
＜耐水性紙の作製＞
塗工液Ｏを上記（ｑ）の塗工液Ｑに変更した以外は実施例３８と同様にして、耐水性紙を作製した。
[Example 43]
(k) Coating Liquid K was prepared in the same manner as in Example 9.
(q) Coating liquid Q was prepared in the same manner as in Example 30.
<Preparation of water-resistant paper>
Water-resistant paper was produced in the same manner as in Example 38, except that the coating liquid O was changed to the coating liquid Q of the above (q).
［実施例４４］
実施例９と同様に（ｋ）塗工液Ｋを作製した。
実施例１１と同様に（ｍ）塗工液Ｍを作製した。
＜耐水性紙の作製＞
塗工液Ｏを上記（ｍ）の塗工液Ｍに変更した以外は実施例３８と同様にして、耐水性紙を作製した。
[Example 44]
(k) Coating Liquid K was prepared in the same manner as in Example 9.
(m) Coating Liquid M was prepared in the same manner as in Example 11.
<Preparation of water-resistant paper>
Water-resistant paper was produced in the same manner as in Example 38, except that the coating liquid O was changed to the coating liquid M of (m) above.
［実施例４５］
実施例９と同様に（ｋ）塗工液Ｋを作製した。
実施例１２と同様に（ｎ）塗工液Ｎを作製した。
＜耐水性紙の作製＞
塗工液Ｏを上記（ｎ）の塗工液Ｎに変更した以外は実施例３８と同様にして、耐水性紙を作製した。
[Example 45]
(k) Coating Liquid K was prepared in the same manner as in Example 9.
(n) Coating Liquid N was prepared in the same manner as in Example 12.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 38, except that the coating liquid O was changed to the coating liquid N of (n) above.
［実施例４６］
坪量が２４６ｇ／ｍ２、紙厚が２７４μｍの紙基材に変更した以外は、実施例４２と同様にして、耐水性紙を作製した。
[Example 46]
Water-resistant paper was produced in the same manner as in Example 42, except that the basis weight was changed to 246 g/m 2 and the paper thickness was changed to 274 μm.
［比較例１］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
実施例３と同様に（ｄ）塗工液Ｄを作製した。
＜耐水性紙の作製＞
塗工液Ｂを上記（ｄ）の塗工液Ｄに変更した以外は実施例１と同様にして、耐水性紙を作製した。
[Comparative Example 1]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(d) Coating Liquid D was prepared in the same manner as in Example 3.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 1, except that the coating liquid B was changed to the coating liquid D of (d) above.
［比較例２］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
（ｇ）塗工液Ｇの作製
エチレン－メタクリル酸共重合体アイオノマーに、ＨＤＰＥと消泡剤を配合して、固形分中のエチレン－メタクリル酸共重合体アイオノマーの含有量が５４．９質量％、ＨＤＰＥの含有量が４４．０質量％であり、消泡剤の含有量が１．１質量％であり、固形分濃度３０質量％の塗工液Ｇを調製した。
[Comparative Example 2]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(g) Preparation of coating liquid G Ethylene-methacrylic acid copolymer ionomer was blended with HDPE and an antifoaming agent so that the content of ethylene-methacrylic acid copolymer ionomer in the solid content was 54.9% by mass. , the content of HDPE was 44.0% by mass, the content of the antifoaming agent was 1.1% by mass, and the solid content concentration was 30% by mass.
＜耐水性紙の作製＞
塗工液Ｂを上記（ｇ）の塗工液Ｇに変更した以外は実施例１と同様にして、耐水性紙を作製した。
<Preparation of water-resistant paper>
Water-resistant paper was produced in the same manner as in Example 1, except that the coating liquid B was changed to the coating liquid G of the above (g).
［比較例３］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
実施例３と同様に（ｄ）塗工液Ｄを作製した。
比較例２と同様に（ｇ）塗工液Ｇを作製した。
＜耐水性紙の作製＞
塗工液Ｂを上記（ｇ）の塗工液Ｇに変更した以外は実施例３と同様にして、耐水性紙を作製した。
[Comparative Example 3]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(d) Coating Liquid D was prepared in the same manner as in Example 3.
(g) Coating Liquid G was prepared in the same manner as in Comparative Example 2.
<Preparation of water-resistant paper>
Water-resistant paper was produced in the same manner as in Example 3, except that the coating liquid B was changed to the coating liquid G of the above (g).
［比較例４］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
実施例３と同様に（ｄ）塗工液Ｄを作製した。
（ｈ）塗工液Ｈの作製
エチレン－メタクリル酸共重合体アイオノマーに、カオリンと消泡剤を配合して、固形分中のエチレン－メタクリル酸共重合体アイオノマーの含有量が７８．７質量％、カオリンの含有量が１９．７質量％であり、消泡剤の含有量が１．６質量％であり、固形分濃度３０質量％の塗工液Ｈを調製した。
＜耐水性紙の作製＞
塗工液Ｂを上記（ｈ）の塗工液Ｈに変更した以外は実施例３と同様にして、耐水性紙を作製した。
[Comparative Example 4]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(d) Coating Liquid D was prepared in the same manner as in Example 3.
(h) Preparation of Coating Liquid H Ethylene-methacrylic acid copolymer ionomer was blended with kaolin and an antifoaming agent so that the content of ethylene-methacrylic acid copolymer ionomer in the solid content was 78.7% by mass. , the content of kaolin was 19.7% by mass, the content of the antifoaming agent was 1.6% by mass, and a coating liquid H having a solid content concentration of 30% by mass was prepared.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 3, except that the coating liquid B was changed to the coating liquid H of the above (h).
［比較例５］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
実施例９と同様に（ｋ）塗工液Ｋを作製した。
（ｒ）塗工液Ｒの作製
エチレン－メタクリル酸共重合体アイオノマーに、低分子量ＰＥと消泡剤を配合して、固形分中のエチレン－メタクリル酸共重合体アイオノマーの含有量が５８．４質量％、低分子量ＰＥの含有量が４１．０質量％であり、消泡剤の含有量が０．６質量％であり、固形分濃度３０質量％の塗工液Ｒを調製した。
＜耐水性紙の作製＞
塗工液Ｌを上記（ｒ）の塗工液Ｒに変更した以外は実施例９と同様にして、耐水性紙を作製した。
[Comparative Example 5]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(k) Coating Liquid K was prepared in the same manner as in Example 9.
(r) Preparation of coating liquid R Ethylene-methacrylic acid copolymer ionomer was blended with low molecular weight PE and an antifoaming agent so that the content of ethylene-methacrylic acid copolymer ionomer in the solid content was 58.4. %, the content of low molecular weight PE was 41.0% by mass, the content of defoaming agent was 0.6% by mass, and the solid content concentration was 30% by mass.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 9, except that the coating liquid L was changed to the coating liquid R of the above (r).
［比較例６］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
（ｉ）塗工液Ｉの作製
エチレン－アクリル酸共重合体アイオノマーに、ＨＤＰＥと消泡剤を配合して、固形分中のエチレン－アクリル酸共重合体アイオノマーの含有量が９４．３質量％、ＨＤＰＥの含有量が３．８質量％であり、消泡剤の含有量が１．９質量％であり、固形分濃度２０質量％の塗工液Ｉを調製した。
＜耐水性紙の作製＞
塗工液Ｂを上記（ｉ）の塗工液Ｉに変更した以外は実施例１と同様にして、耐水性紙を作製した。
[Comparative Example 6]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(i) Preparation of coating liquid I Ethylene-acrylic acid copolymer ionomer was blended with HDPE and an antifoaming agent so that the content of ethylene-acrylic acid copolymer ionomer in the solid content was 94.3% by mass. , the content of HDPE was 3.8% by mass, the content of the antifoaming agent was 1.9% by mass, and the solid content concentration was 20% by mass.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 1, except that the coating liquid B was changed to the coating liquid I of (i) above.
［比較例７］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
比較例６と同様に（ｉ）塗工液Ｉを作製した。
（ｊ）塗工液Ｊの作製
エチレン－アクリル酸共重合体アイオノマーに、消泡剤を配合して、固形分中のエチレン－アクリル酸共重合体アイオノマーの含有量が９８．０質量％、消泡剤の含有量が２．０質量％であり、固形分濃度２０質量％の塗工液Ｊを調製した。
[Comparative Example 7]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(i) Coating liquid I was prepared in the same manner as in Comparative Example 6.
(j) Preparation of coating liquid J Ethylene-acrylic acid copolymer ionomer is blended with an antifoaming agent so that the content of ethylene-acrylic acid copolymer ionomer in the solid content is 98.0% by mass. A coating liquid J having a foaming agent content of 2.0% by mass and a solid concentration of 20% by mass was prepared.
＜耐水性紙の作製＞
塗工液Ｄを上記（ｊ）の塗工液Ｊに、塗工液Ｂを上記（ｉ）の塗工液Ｉに変更した以外は実施例３と同様にして、耐水性紙を作製した。
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 3, except that the coating liquid D was changed to the coating liquid J of the above (j), and the coating liquid B was changed to the coating liquid I of the above (i).
［比較例８］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
実施例３と同様に（ｄ）塗工液Ｄを作製した。
＜耐水性紙の作製＞
塗工液Ｂを上記（ｄ）の塗工液Ｄに変更した以外は実施例１３と同様にして、耐水性紙を作製した。
[Comparative Example 8]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(d) Coating Liquid D was prepared in the same manner as in Example 3.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 13, except that the coating liquid B was changed to the coating liquid D of the above (d).
［比較例９］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
実施例３と同様に（ｄ）塗工液Ｄを作製した。
実施例３と同様に（ｇ）塗工液Ｇを作製した。
＜耐水性紙の作製＞
塗工液Ｂを上記（ｇ）の塗工液Ｇに変更した以外は実施例１３と同様にして、耐水性紙を作製した。
[Comparative Example 9]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(d) Coating Liquid D was prepared in the same manner as in Example 3.
(g) Coating Liquid G was prepared in the same manner as in Example 3.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 13, except that the coating liquid B was changed to the coating liquid G of the above (g).
［比較例１０］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
実施例３と同様に（ｄ）塗工液Ｄを作製した。
実施例３と同様に（ｇ）塗工液Ｇを作製した。
＜耐水性紙の作製＞
塗工液Ｂを上記（ｇ）の塗工液Ｇに変更した以外は実施例１５と同様にして、耐水性紙を作製した。
[Comparative Example 10]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(d) Coating Liquid D was prepared in the same manner as in Example 3.
(g) Coating Liquid G was prepared in the same manner as in Example 3.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 15, except that the coating liquid B was changed to the coating liquid G of the above (g).
［比較例１１］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
実施例３と同様に（ｄ）塗工液Ｄを作製した。
比較例４と同様に（ｈ）塗工液Ｈを作製した。
＜耐水性紙の作製＞
塗工液Ｂを上記（ｈ）の塗工液Ｈに変更した以外は実施例１５と同様にして、耐水性紙を作製した。
[Comparative Example 11]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(d) Coating Liquid D was prepared in the same manner as in Example 3.
(h) Coating Liquid H was prepared in the same manner as in Comparative Example 4.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 15, except that the coating liquid B was changed to the coating liquid H of the above (h).
［比較例１２］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
実施例９と同様に（ｋ）塗工液Ｋを作製した。
比較例５と同様に（ｒ）塗工液Ｒを作製した。
＜耐水性紙の作製＞
塗工液Ｌを上記（ｒ）の塗工液Ｒに変更した以外は実施例２１と同様にして、耐水性紙を作製した。
[Comparative Example 12]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(k) Coating Liquid K was prepared in the same manner as in Example 9.
(r) Coating Liquid R was prepared in the same manner as in Comparative Example 5.
<Preparation of water-resistant paper>
Water-resistant paper was produced in the same manner as in Example 21, except that the coating liquid L was changed to the coating liquid R of the above (r).
［比較例１３］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
比較例７と同様に（ｊ）塗工液Ｊを作製した。
比較例６と同様に（ｉ）塗工液Ｉを作製した。
＜耐水性紙の作製＞
塗工液Ｄを上記（ｊ）の塗工液Ｊに、塗工液Ｂを上記（ｉ）の塗工液Ｉに変更した以外は実施例１３と同様にして、耐水性紙を作製した。
[Comparative Example 13]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(j) Coating Liquid J was prepared in the same manner as in Comparative Example 7.
(i) Coating liquid I was prepared in the same manner as in Comparative Example 6.
<Preparation of water-resistant paper>
Water-resistant paper was prepared in the same manner as in Example 13, except that the coating liquid D was changed to the coating liquid J of the above (j), and the coating liquid B was changed to the coating liquid I of the above (i).
［比較例１４］
実施例１と同様に（ａ）顔料層塗工液Ａを作製した。
比較例７と同様に（ｊ）塗工液Ｊを作製した。
比較例６と同様に（ｉ）塗工液Ｉを作製した。
＜耐水性紙の作製＞
表面の塗工液Ｄを上記（ｊ）の塗工液Ｊに、裏面の塗工液Ｂを上記（ｉ）の塗工液Ｉに変更した以外は実施例１５と同様にして、耐水性紙を作製した。
[Comparative Example 14]
In the same manner as in Example 1, (a) pigment layer coating solution A was prepared.
(j) Coating Liquid J was prepared in the same manner as in Comparative Example 7.
(i) Coating liquid I was prepared in the same manner as in Comparative Example 6.
<Preparation of water-resistant paper>
Water-resistant paper was prepared in the same manner as in Example 15 except that the coating solution D for the front surface was changed to the coating solution J in (j) above, and the coating solution B for the back surface was changed to the coating solution I in (i) above. was made.
［比較例１５］
実施例３と同様に（ｄ）塗工液Ｄを作製した。
＜耐水性紙の作製＞
塗工液Ｏを上記（ｄ）の塗工液Ｄに変更した以外は実施例２５と同様にして、耐水性紙を作製した。
[Comparative Example 15]
(d) Coating Liquid D was prepared in the same manner as in Example 3.
<Preparation of water-resistant paper>
Water-resistant paper was produced in the same manner as in Example 25, except that the coating liquid O was changed to the coating liquid D of (d) above.
［比較例１６］
比較例２と同様に（ｇ）塗工液Ｇを作製した。
＜耐水性紙の作製＞
塗工液Ｏを上記（ｇ）の塗工液Ｇに変更した以外は実施例２５と同様にして、耐水性紙を作製した。
[Comparative Example 16]
(g) Coating Liquid G was prepared in the same manner as in Comparative Example 2.
<Preparation of water-resistant paper>
A water-resistant paper was produced in the same manner as in Example 25, except that the coating liquid O was changed to the coating liquid G of (g) above.
［比較例１７］
実施例３と同様に（ｄ）塗工液Ｄを作製した。
比較例２と同様に（ｇ）塗工液Ｇを作製した。
＜耐水性紙の作製＞
塗工液Ｋを上記（ｄ）の塗工液Ｄに、塗工液Ｏを上記（ｇ）の塗工液Ｇに、変更した以外は実施例２７と同様にして、耐水性紙を作製した。
[Comparative Example 17]
(d) Coating Liquid D was prepared in the same manner as in Example 3.
(g) Coating Liquid G was prepared in the same manner as in Comparative Example 2.
<Preparation of water-resistant paper>
A water-resistant paper was produced in the same manner as in Example 27, except that the coating liquid K was changed to the coating liquid D of the above (d), and the coating liquid O was changed to the coating liquid G of the above (g). .
［比較例１８］
実施例３と同様に（ｄ）塗工液Ｄを作製した。
比較例４と同様に（ｈ）塗工液Ｈを作製した。
＜耐水性紙の作製＞
塗工液Ｋを上記（ｄ）の塗工液Ｄに、塗工液Ｏを上記（ｈ）の塗工液Ｈに、変更した以外は実施例２７と同様にして、耐水性紙を作製した。
[Comparative Example 18]
(d) Coating Liquid D was prepared in the same manner as in Example 3.
(h) Coating Liquid H was prepared in the same manner as in Comparative Example 4.
<Preparation of water-resistant paper>
Water-resistant paper was produced in the same manner as in Example 27, except that the coating liquid K was changed to the coating liquid D of the above (d), and the coating liquid O was changed to the coating liquid H of the above (h). .
［比較例１９］
実施例９と同様に（ｋ）塗工液Ｋを作製した。
比較例５と同様に（ｒ）塗工液Ｒを作製した。
＜耐水性紙の作製＞
塗工液Ｏを上記（ｒ）の塗工液Ｒに変更した以外は実施例２７と同様にして、耐水性紙を作製した。
[Comparative Example 19]
(k) Coating Liquid K was prepared in the same manner as in Example 9.
(r) Coating Liquid R was prepared in the same manner as in Comparative Example 5.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 27, except that the coating liquid O was changed to the coating liquid R of the above (r).
［比較例２０］
比較例１３と同様に（ｉ）塗工液Ｉを作製した。
＜耐水性紙の作製＞
塗工液Ｏを上記（ｉ）の塗工液Ｉに変更した以外は実施例２５と同様にして、耐水性紙を作製した。
[Comparative Example 20]
(i) Coating liquid I was prepared in the same manner as in Comparative Example 13.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 25, except that the coating liquid O was changed to the coating liquid I of (i) above.
［比較例２１］
比較例６と同様に（ｉ）塗工液Ｉを作製した。
比較例７と同様に（ｊ）塗工液Ｊを作製した。
＜耐水性紙の作製＞
塗工液Ｋを上記（ｊ）の塗工液Ｊに、塗工液Ｏを上記（ｉ）の塗工液Ｉに、変更した以外は実施例２７と同様にして、耐水性紙を作製した。
[Comparative Example 21]
(i) Coating liquid I was prepared in the same manner as in Comparative Example 6.
(j) Coating Liquid J was prepared in the same manner as in Comparative Example 7.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 27, except that the coating liquid K was changed to the coating liquid J of the above (j), and the coating liquid O was changed to the coating liquid I of the above (i). .
［比較例２２］
実施例９と同様に（ｋ）塗工液Ｋを作製した。
＜耐水性紙の作製＞
塗工液Ｏを上記（ｋ）の塗工液Ｋに変更した以外は実施例３６と同様にして、耐水性紙を作製した。
[Comparative Example 22]
(k) Coating Liquid K was prepared in the same manner as in Example 9.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 36, except that the coating liquid O was changed to the coating liquid K of the above (k).
［比較例２３］
実施例９と同様に（ｋ）塗工液Ｋを作製した。
比較例２と同様に（ｇ）塗工液Ｇを作製した。
＜耐水性紙の作製＞
塗工液Ｏを上記（ｇ）の塗工液Ｇに変更した以外は実施例３６と同様にして、耐水性紙を作製した。
[Comparative Example 23]
(k) Coating Liquid K was prepared in the same manner as in Example 9.
(g) Coating Liquid G was prepared in the same manner as in Comparative Example 2.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 36, except that the coating liquid O was changed to the coating liquid G of the above (g).
［比較例２４］
実施例９と同様に（ｋ）塗工液Ｋを作製した。
比較例２と同様に（ｇ）塗工液Ｇを作製した。
＜耐水性紙の作製＞
塗工液Ｏを上記（ｇ）の塗工液Ｇに変更した以外は実施例３８と同様にして、耐水性紙を作製した。
[Comparative Example 24]
(k) Coating Liquid K was prepared in the same manner as in Example 9.
(g) Coating Liquid G was prepared in the same manner as in Comparative Example 2.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 38, except that the coating liquid O was changed to the coating liquid G of the above (g).
［比較例２５］
実施例９と同様に（ｋ）塗工液Ｋを作製した。
比較例４と同様に（ｈ）塗工液Ｈを作製した。
＜耐水性紙の作製＞
塗工液Ｏを上記（ｈ）の塗工液Ｈに、変更した以外は実施例３８と同様にして、耐水性紙を作製した。
[Comparative Example 25]
(k) Coating Liquid K was prepared in the same manner as in Example 9.
(h) Coating Liquid H was prepared in the same manner as in Comparative Example 4.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 38, except that the coating liquid O was changed to the coating liquid H of the above (h).
［比較例２６］
実施例９と同様に（ｋ）塗工液Ｋを作製した。
比較例１３と同様に（ｒ）塗工液Ｒを作製した。
＜耐水性紙の作製＞
塗工液Ｏを上記（ｒ）の塗工液Ｒに変更した以外は実施例３８と同様にして、耐水性紙を作製した。
[Comparative Example 26]
(k) Coating Liquid K was prepared in the same manner as in Example 9.
(r) Coating Liquid R was prepared in the same manner as in Comparative Example 13.
<Preparation of water-resistant paper>
Water-resistant paper was produced in the same manner as in Example 38, except that the coating liquid O was changed to the coating liquid R of the above (r).
［比較例２７］
比較例６と同様に（ｉ）塗工液Ｉを作製した。
比較例７と同様に（ｊ）塗工液Ｊを作製した。
＜耐水性紙の作製＞
塗工液Ｋを上記（ｊ）の塗工液Ｊに、塗工液Ｏを上記（ｉ）の塗工液Ｉに、変更した以外は実施例３６と同様にして、耐水性紙を作製した。
[Comparative Example 27]
(i) Coating liquid I was prepared in the same manner as in Comparative Example 6.
(j) Coating Liquid J was prepared in the same manner as in Comparative Example 7.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 36, except that the coating liquid K was changed to the coating liquid J of the above (j), and the coating liquid O was changed to the coating liquid I of the above (i). .
［比較例２８］
比較例６と同様に（ｉ）塗工液Ｉを作製した。
比較例７と同様に（ｊ）塗工液Ｊを作製した。
＜耐水性紙の作製＞
塗工液Ｋを上記（ｊ）の塗工液Ｊに、塗工液Ｏを上記（ｉ）の塗工液Ｉに、変更した以外は実施例３８と同様にして、耐水性紙を作製した。
[Comparative Example 28]
(i) Coating liquid I was prepared in the same manner as in Comparative Example 6.
(j) Coating Liquid J was prepared in the same manner as in Comparative Example 7.
<Preparation of water-resistant paper>
A water-resistant paper was prepared in the same manner as in Example 38, except that the coating liquid K was changed to the coating liquid J of the above (j), and the coating liquid O was changed to the coating liquid I of the above (i). .
［評価方法］
＜透気度＞
透気度は、ＪＩＳ Ｐ ８１１７：２００９に準拠して測定した。
[Evaluation method]
<Air Permeability>
The air permeability was measured according to JIS P 8117:2009.
＜粘着力＞
裏面にタッキング試験機ＴＡＣ－１０００（株式会社レスカ製）のプローブを接触させ測定した。押付け速度０．５ｍｍ／ｓ、押付け荷重２００ｇｆ、押付け時間１ｓ、引き上げ速度１ｍｍ／ｓとし、ステージ温度を９０℃、プローブ温度を２５℃とした。
なお、粘着力が高いと、製造時などにロールへの貼り付きが生じやすく、また、ロール汚れ発生の原因となりやすい。
Ａ：測定の平均値が２０ｇｆ以下 表面べたつきがない
Ｂ：測定の平均値が２０ｇｆを超え４０ｇｆ以下 表面べたつきが少ない
Ｃ：測定の平均値が４０ｇｆを超え６０ｇｆ以下 表面が少しべたつく
Ｄ：測定の平均値が６０ｇｆを超える 表面がべたつく
<Adhesive strength>
A probe of a tacking tester TAC-1000 (manufactured by Resca Co., Ltd.) was brought into contact with the back surface to measure. The pressing speed was 0.5 mm/s, the pressing load was 200 gf, the pressing time was 1 s, the lifting speed was 1 mm/s, the stage temperature was 90°C, and the probe temperature was 25°C.
If the adhesive strength is high, it tends to stick to rolls during production, and tends to cause roll stains.
A: Average value of measurement is 20 gf or less, no surface stickiness B: Average value of measurement is more than 20 gf and less than 40 gf, less surface stickiness C: Average value of measurement is more than 40 gf and less than 60 gf, surface is slightly sticky D: Average of measurement The value exceeds 60 gf The surface becomes sticky
＜Ｃｏｂｂ吸水度＞
Ｃｏｂｂ吸水度は、得られた耐水性紙を２０℃の水、または９０℃の温水に３０分間接触させ、接触前後の質量差から、ＪＩＳ Ｐ ８１４０：１９９８に準拠して測定した。
<Cobb water absorption>
The Cobb water absorbency was measured according to JIS P 8140:1998 by contacting the resulting water-resistant paper with water at 20°C or hot water at 90°C for 30 minutes and measuring the difference in mass before and after contact.
＜ヒートシール性＞
サンプルを２．５ｃｍ×１５ｃｍにカットし、塗工面（表面）と塗工面（裏面）、または塗工面（表面）と紙基材面（裏面）が密着するように重ね合わせたのち、ヒートシールテスター（テスター産業株式会社製）を用いて、温度１５０℃または２５０℃、圧力０．２ＭＰａで２秒間ヒートシールした後、室温まで冷却した。その後、重ねたサンプルを手で剥がした時の様子を下記評価基準に基づいて評価した。
Ａ：完全に接着しており、手で簡単に剥がすことが困難である
Ｂ：接着しているが、接着強度が弱く、手で簡単に剥がすことができる
Ｃ：少なくとも一部に接着していない箇所がある
<Heat sealability>
Cut the sample into 2.5 cm x 15 cm, and put the coated surface (surface) and the coated surface (back), or the coated surface (surface) and the paper substrate surface (back) so that they are in close contact with each other, and then use a heat seal tester. (manufactured by Tester Sangyo Co., Ltd.), it was heat-sealed at a temperature of 150° C. or 250° C. and a pressure of 0.2 MPa for 2 seconds, and then cooled to room temperature. After that, the state when the stacked samples were peeled off by hand was evaluated based on the following evaluation criteria.
A: Completely adhered and difficult to peel off easily by hand B: Adhered, but adhesive strength is weak and can be easily peeled off by hand C: Not adhered to at least part there is a point
＜耐ブロッキング性＞
サンプルを５ｃｍ角にカットし、表面と裏面（片面塗工の場合は紙基材）が密着するように重ね合わせ、ブロッキングテスターに挟んで６５℃にて３０分加熱後、圧力０．５ｋｇ／ｃｍ２で３０分加圧した。室温まで冷却後に下記の通り評価した。
Ａ：抵抗なく剥がれる
Ｂ：僅かに抵抗がある
Ｃ：抵抗が大きく、塗工面が僅かに剥がれる
Ｄ：かなりの抵抗があり塗工面が剥がれる（紙剥けがある）
<Blocking resistance>
The sample is cut into 5 cm squares, overlapped so that the front and back surfaces (paper base material in the case of single-sided coating) are in close contact, sandwiched between blocking testers and heated at 65 ° C. for 30 minutes, and the pressure is 0.5 kg / cm. Pressurized at 2 for 30 minutes. After cooling to room temperature, it was evaluated as follows.
A: Peeled off without resistance B: Slightly resisted C: Resistance is large, the coated surface is slightly peeled D: There is considerable resistance, and the coated surface is peeled off (there is paper peeling)
エチレン－メタクリル酸共重合体および有機粒子を含有し、有機粒子の含有量４０質量％以下である耐水性層を有する実施例１～４６では、透気度が高く、耐水性に優れ、さらに、耐ブロッキング性にも優れ、ヒートシール性を有する耐水性紙が得られた。
一方、耐水性層が有機粒子を含有しない、比較例１、８、１５、および２２では、耐ブロッキング性および粘着力が悪化していた。また、有機粒子の含有量が４０質量％を超える比較例２、３、５、９、１０、１２、１６、１７、１９、２３、２４、および２６では、十分なヒートシール性が得られなかった。さらに、有機粒子の代わりに、無機粒子であるカオリンを使用した比較例４、１１、１８、および２５では、耐水性に劣り、特に９０℃の熱水に対して、十分な耐水性が得られなかった。また、実施例に比べて、表面に粘着性があった。
樹脂成分としてエチレン－メタクリル酸共重合体の代わりにエチレン－アクリル酸共重合体を使用した比較例６、７、１３、１４、２０、２１、２７、および２８では、十分な耐ブロッキング性が得られなかった。
In Examples 1 to 46, which contain an ethylene-methacrylic acid copolymer and organic particles and have a water-resistant layer with an organic particle content of 40% by mass or less, air permeability is high, water resistance is excellent, and further, A water-resistant paper having excellent blocking resistance and heat-sealing properties was obtained.
On the other hand, in Comparative Examples 1, 8, 15, and 22, in which the water-resistant layer did not contain organic particles, the blocking resistance and adhesive strength were poor. In addition, in Comparative Examples 2, 3, 5, 9, 10, 12, 16, 17, 19, 23, 24, and 26, in which the content of organic particles exceeds 40% by mass, sufficient heat-sealability was not obtained. rice field. Furthermore, in Comparative Examples 4, 11, 18, and 25, in which kaolin, which is an inorganic particle, was used instead of the organic particles, the water resistance was poor, and sufficient water resistance was obtained particularly against hot water at 90°C. I didn't. In addition, the surface was sticky compared to the examples.
In Comparative Examples 6, 7, 13, 14, 20, 21, 27, and 28 in which ethylene-acrylic acid copolymer was used instead of ethylene-methacrylic acid copolymer as the resin component, sufficient blocking resistance was obtained. I couldn't.
Claims (16)
該耐水性層が、エチレン－メタクリル酸共重合体、および有機粒子を含有し、
該有機粒子の融点または軟化点が１００℃以上であり、
耐水性層中の有機粒子の含有量が４０質量％以下である、
耐水性紙。 A water-resistant paper having a water-resistant layer as the top layer on at least one surface of the paper substrate,
The water-resistant layer contains an ethylene-methacrylic acid copolymer and organic particles,
The organic particles have a melting point or softening point of 100° C. or higher,
The content of organic particles in the water-resistant layer is 40% by mass or less,
water resistant paper.
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