JP2021155886A - Water resistant agent kit for paper making, water resistant paper, and method of producing the same - Google Patents
Water resistant agent kit for paper making, water resistant paper, and method of producing the same Download PDFInfo
- Publication number
- JP2021155886A JP2021155886A JP2020057425A JP2020057425A JP2021155886A JP 2021155886 A JP2021155886 A JP 2021155886A JP 2020057425 A JP2020057425 A JP 2020057425A JP 2020057425 A JP2020057425 A JP 2020057425A JP 2021155886 A JP2021155886 A JP 2021155886A
- Authority
- JP
- Japan
- Prior art keywords
- water resistant
- paper
- agent
- resistant agent
- fluorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000013053 water resistant agent Substances 0.000 title claims abstract description 136
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 238000000034 method Methods 0.000 title claims description 28
- 239000000463 material Substances 0.000 claims abstract description 79
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 78
- 239000011737 fluorine Substances 0.000 claims abstract description 78
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229920006317 cationic polymer Polymers 0.000 claims abstract description 70
- 239000000701 coagulant Substances 0.000 claims abstract description 70
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 64
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims description 27
- 229920001577 copolymer Polymers 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 22
- 125000002091 cationic group Chemical group 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000004952 Polyamide Substances 0.000 claims description 10
- 229920002647 polyamide Polymers 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 9
- 229920000768 polyamine Polymers 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 229920002050 silicone resin Polymers 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- 239000011436 cob Substances 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- -1 polyvinylamines Polymers 0.000 claims description 4
- 229920003002 synthetic resin Polymers 0.000 claims description 4
- RIHRKDVNDFVRGD-UHFFFAOYSA-N CNC.NCCN Chemical compound CNC.NCCN RIHRKDVNDFVRGD-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- 229920002396 Polyurea Polymers 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229920006319 cationized starch Polymers 0.000 claims description 3
- 239000000412 dendrimer Substances 0.000 claims description 3
- 229920000736 dendritic polymer Polymers 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 239000012948 isocyanate Substances 0.000 claims description 3
- 150000002513 isocyanates Chemical class 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 229920000083 poly(allylamine) Polymers 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920005573 silicon-containing polymer Polymers 0.000 claims description 3
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 claims description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 239000000123 paper Substances 0.000 description 184
- 239000002585 base Substances 0.000 description 19
- 239000013055 pulp slurry Substances 0.000 description 17
- 239000010893 paper waste Substances 0.000 description 15
- 239000002002 slurry Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 12
- 229920001131 Pulp (paper) Polymers 0.000 description 10
- 125000000129 anionic group Chemical group 0.000 description 9
- 239000000835 fiber Substances 0.000 description 9
- 238000004537 pulping Methods 0.000 description 9
- 238000004513 sizing Methods 0.000 description 8
- 238000004448 titration Methods 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 5
- 239000002655 kraft paper Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- 239000005871 repellent Substances 0.000 description 4
- 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 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000010897 cardboard waste Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 230000002940 repellent Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 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 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000013054 paper strength agent Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000008104 plant cellulose Substances 0.000 description 2
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011122 softwood Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- FEIQOMCWGDNMHM-UHFFFAOYSA-N 5-phenylpenta-2,4-dienoic acid Chemical compound OC(=O)C=CC=CC1=CC=CC=C1 FEIQOMCWGDNMHM-UHFFFAOYSA-N 0.000 description 1
- 241001133760 Acoelorraphe Species 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 244000273256 Phragmites communis Species 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229920006243 acrylic copolymer Polymers 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 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
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012470 diluted sample Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- WZAPMUSQALINQD-UHFFFAOYSA-M potassium;ethenyl sulfate Chemical compound [K+].[O-]S(=O)(=O)OC=C WZAPMUSQALINQD-UHFFFAOYSA-M 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Landscapes
- Paper (AREA)
Abstract
Description
本発明は、抄紙用耐水剤キット、耐水紙及びその製造方法に関する。 The present invention relates to a water resistant agent kit for papermaking, water resistant paper, and a method for producing the same.
耐水紙、耐油紙など、耐水性や耐油性などが付与された紙が様々な分野で使用されている。このような改質した紙の製造方法としては、様々な方法が提案されている。 Paper with water resistance and oil resistance, such as water resistant paper and oil resistant paper, is used in various fields. Various methods have been proposed as a method for producing such modified paper.
例えば、特許文献１には、紙基体に、少なくとも（メタ）アクリル酸のＣ12〜Ｃ40アルキルエステルを重合単位として有するポリマーをコーティングする、紙基体の改質方法が提案されている。 For example, Patent Document 1 proposes a method for modifying a paper substrate by coating the paper substrate with a polymer having at least C 12 to C 40 alkyl esters of (meth) acrylic acid as a polymerization unit.
また、特許文献２には、耐油層のうち少なくとも１層中にメタクリル酸−アクリル酸アルキルエステル−スチレン共重合体撥水剤を含有させた撥水耐油紙が提案されている。 Further, Patent Document 2 proposes a water-repellent oil-resistant paper in which at least one of the oil-resistant layers contains a methacrylic acid-acrylic acid alkyl ester-styrene copolymer water repellent.
また、特許文献３には、紙中にガラス転移点２０℃以上の合成樹脂及び撥水剤から成る樹脂成分を含有し、該樹脂成分の含有率が２質量％以上３０質量％未満で、かつ合成樹脂／撥水剤の重量比が８０／２０〜９８／２である樹脂含有紙が提案されている。 Further, Patent Document 3 contains a resin component composed of a synthetic resin having a glass transition point of 20 ° C. or higher and a water repellent in the paper, and the content of the resin component is 2% by mass or more and less than 30% by mass. A resin-containing paper having a weight ratio of synthetic resin / water repellent of 80/20 to 98/2 has been proposed.
さらに、特許文献４には、セルロース系基体に、エチレン系熱可塑性ポリマーと、少なくとも１種の高分子安定剤との溶融混錬物の水性分散体を塗工した、耐油脂性、耐水性、透湿性のいずれかに優れる塗工セルロース物品が提案されている。 Further, in Patent Document 4, a cellulose-based substrate is coated with an aqueous dispersion of a melt-kneaded product of an ethylene-based thermoplastic polymer and at least one polymer stabilizer, which is oil-resistant, water-resistant, and transparent. Coated cellulose articles having excellent wettability have been proposed.
本発明は、抄紙に利用することによって耐水紙を好適に製造することができる、抄紙用耐水剤キットを提供することを主な目的とする。また、本発明は、抄紙用耐水剤キットを利用した耐水紙の製造方法、及び耐水紙を提供することも目的とする。 A main object of the present invention is to provide a water resistant agent kit for paper making, which can suitably produce water resistant paper by using it for paper making. Another object of the present invention is to provide a method for producing a water resistant paper using a water resistant agent kit for papermaking, and to provide the water resistant paper.
本発明者らは、前記課題を解決するために鋭意検討した。その結果、カチオン性高分子凝結剤からなる第１剤と、非フッ素系耐水剤からなる第２剤とを備えるキットを調製し、当該キットを利用し、用時に紙料と前記第１剤及び前記第２剤を順次混合して、紙料を抄紙することにより、紙基材に対して耐水性を好適に付与できることを見出した。さらに、カチオン電荷密度が特定範囲内のカチオン性高分子凝結剤を利用すると、非フッ素系耐水剤がアニオン性であってもカチオン性であっても、紙基材に対して耐水性を好適に付与できることも見出した。また、古紙含有率の高い紙料（すなわち、微細繊維の含有率が高い紙料）を用いた場合にも、紙基材に対して耐水性を好適に付与できることも見出した。本発明は、このような知見に基づき、さらに鋭意検討を重ねて完成した発明である。 The present inventors have diligently studied to solve the above-mentioned problems. As a result, a kit including a first agent made of a cationic polymer coagulant and a second agent made of a non-fluorine-based water resistant agent was prepared, and the kit was used to prepare a paper material and the first agent and the first agent at the time of use. It has been found that water resistance can be suitably imparted to a paper substrate by sequentially mixing the second agent and making a paper material. Further, when a cationic polymer coagulant having a cationic charge density within a specific range is used, the water resistance of the non-fluorine-based water resistant agent is preferably anionic or cationic, with respect to the paper substrate. I also found that it can be granted. It was also found that water resistance can be suitably imparted to the paper base material even when a paper material having a high content of used paper (that is, a paper material having a high content of fine fibers) is used. The present invention is an invention completed through further diligent studies based on such findings.
すなわち、本発明は、下記の構成を備える発明を提供する。
項１． カチオン性高分子凝結剤からなる第１剤と、
非フッ素系耐水剤からなる第２剤と、
を備え、
用時に紙料と前記第１剤及び前記第２剤を順次混合して、紙料が抄紙された紙基材に耐水性を付与するための、抄紙用耐水剤キット。
項２． 前記非フッ素系耐水剤の電荷密度が、−１００．０〜＋２００．０μｅｑ／ｇである、項１に記載の抄紙用耐水剤キット。
項３． 前記非フッ素系耐水剤が、長鎖アクリレート系耐水剤、長鎖アクリレート−シリコーンマクロモノマー共重合体系耐水剤、ハイブリッドエマルション系耐水剤、長鎖アクリレート−ハロゲン化オレフィン共重合体系耐水剤、長鎖アクリレート共重合体と長鎖アルキル変性シリコーン重合体のブレンド系耐水剤、長鎖アクリレート共重合体と塩化ビニル系重合体とシリコーン樹脂のブレンド系耐水剤、アミノ変性シリコーンとシリコーン樹脂と多官能イソシアネートのブレンド系耐水剤、ポリウレタン系耐水剤、ポリ尿素系耐水剤及びポリウレタンデンドリマー系耐水剤からなる群より選択される少なくとも１種である、項１又は２に記載の抄紙用耐水剤キット。
項４． 前記カチオン性高分子凝結剤のカチオン電荷密度が、＋１００．０〜＋１００００．０μｅｑ／ｇである、項１〜３のいずれか１項に記載の抄紙用耐水剤キット。
項５． 前記カチオン性高分子凝結剤が、ポリアミンエピクロロヒドリン樹脂、ポリアミドエピクロロヒドリン樹脂、カチオン化澱粉、カチオン性ポリアクリルアミド、カチオン変性ポリビニルアルコール、ポリジアリルジメチルアンモニウムクロライド又はその誘導体、ジアリルジメチルアンモニウムクロライドと他のモノマーの共重合体、ポリアミン、ポリアリルアミン、ポリビニルアミン、ポリエチレンイミン、２−（メタクリロイルオキシ）エチルトリメチルアンモニウムクロリド重合物、Ｎ−ビニルホルムアミド−ビニルアミン共重合体、メラミン樹脂、ポリアミドエポキシ樹脂、ポリアミドポリアミン樹脂、ジメチルアミンエピクロルヒドリン樹脂及びジメチルアミン−エチレンジアミンエピクロルヒドリン共重合体からなる群より選択される少なくとも１種である、項１〜４のいずれか１項に記載の抄紙用耐水剤キット。
項６． 少なくとも、カチオン性高分子凝結剤及び非フッ素系耐水剤が紙基材に含まれている、耐水紙。
項７． 項１〜５のいずれか１項に記載の抄紙用耐水剤キットを用いて、紙基材が耐水処理されてなる、耐水紙。
項８． ＪＩＳ Ｐ８１４０：１９９８（紙及び板紙−吸水度試験方法−コッブ法）の規定に準拠して測定されるコブ吸水度が、２５．０ｇ／ｍ2以下である、項６又は７に記載の耐水紙。
項９． 前記カチオン性高分子凝結剤及び前記非フッ素系耐水剤の合計含有量が、０．０５〜１０．０ｇ／ｍ2である、項６〜８のいずれか１項に記載の耐水紙。
項１０． 前記カチオン性高分子凝結剤の含有割合が０．０５〜１０．０質量％であり、前記非フッ素系耐水剤の含有割合が０．５〜２０．０質量％である、項６〜９のいずれか１項に記載の耐水紙。
項１１． カチオン性高分子凝結剤からなる第１剤を紙料と混合する工程１と、
前記工程１で得られた混合物と、非フッ素系耐水剤からなる第２剤とを混合する工程２と、
前記工程２で得られた混合物を抄紙する工程３と、
を備える、耐水紙の製造方法。
That is, the present invention provides an invention having the following configuration.
Item 1. The first agent consisting of a cationic polymer coagulant and
A second agent consisting of a non-fluorine-based water resistant agent,
With
A water resistant agent kit for papermaking, which sequentially mixes the paper material with the first agent and the second agent at the time of use to impart water resistance to the paper substrate on which the paper material is made.
Item 2. Item 2. The water resistant kit for papermaking according to Item 1, wherein the non-fluorine-based water resistant agent has a charge density of -100.0 to +200.0 μeq / g.
Item 3. The non-fluorine-based water resistant agent is a long-chain acrylate-based water resistant agent, a long-chain acrylate-silicone macromonomer copolymer-based water resistant agent, a hybrid emulsion-based water resistant agent, a long-chain acrylate-halogenated olefin copolymer system water resistant agent, and a long-chain acrylate. Blend type water resistant agent of copolymer and long chain alkyl modified silicone polymer, blend type water resistant agent of long chain acrylate copolymer, vinyl chloride polymer and silicone resin, blend of amino modified silicone, silicone resin and polyfunctional isocyanate Item 3. The water resistant kit for papermaking according to Item 1 or 2, which is at least one selected from the group consisting of a water resistant agent, a polyurethane water resistant agent, a polyurea water resistant agent, and a polymer dendrimer water resistant agent.
Item 4. Item 3. The water resistant kit for papermaking according to any one of Items 1 to 3, wherein the cationic charge density of the cationic polymer coagulant is +100.0 to +10000.0 μeq / g.
Item 5. The cationic polymer coagulant is a polyamine epichlorohydrin resin, a polyamide epichlorohydrin resin, a cationized starch, a cationic polyacrylamide, a cation-modified polyvinyl alcohol, a polydialyldimethylammonium chloride or a derivative thereof, or a diallyldimethylammonium chloride. And other monomer copolymers, polyamines, polyallylamines, polyvinylamines, polyethyleneimines, 2- (methacryloyloxy) ethyltrimethylammonium chloride polymers, N-vinylformamide-vinylamine copolymers, melamine resins, polyamide epoxy resins, Item 4. The water resistant kit for papermaking according to any one of Items 1 to 4, which is at least one selected from the group consisting of a polyamide polyamine resin, a dimethylamine epichlorohydrin resin and a dimethylamine-ethylenediamine epichlorohydrin copolymer.
Item 6. A water resistant paper in which at least a cationic polymer coagulant and a non-fluorine water resistant agent are contained in a paper base material.
Item 7. A water resistant paper obtained by subjecting a paper base material to a water resistant treatment using the water resistant agent kit for papermaking according to any one of Items 1 to 5.
Item 8. Item 6. The water resistant paper according to Item 6 or 7, wherein the bump water absorption measured in accordance with the provisions of JIS P8140: 1998 (paper and paperboard-water absorption test method-cobb method) is 25.0 g / m 2 or less. ..
Item 9. Item 2. The water resistant paper according to any one of Items 6 to 8, wherein the total content of the cationic polymer coagulant and the non-fluorine-based water resistant agent is 0.05 to 10.0 g / m 2.
Item 10. Item 6-9, wherein the content ratio of the cationic polymer coagulant is 0.05 to 10.0% by mass, and the content ratio of the non-fluorine-based water resistant agent is 0.5 to 20.0% by mass. The water resistant paper according to any one of the items.
Item 11. Step 1 of mixing the first agent consisting of a cationic polymer coagulant with a paper material,
Step 2 of mixing the mixture obtained in the above step 1 with a second agent made of a non-fluorine-based water resistant agent.
Step 3 of papermaking the mixture obtained in step 2 and
A method for manufacturing waterproof paper.
本発明によれば、抄紙に利用することによって耐水紙を好適に製造することができる、抄紙用耐水剤キットを提供することができる。また、本発明によれば、抄紙用耐水剤キットを利用した耐水紙の製造方法、及び耐水紙を提供することもできる。 According to the present invention, it is possible to provide a water resistant agent kit for paper making, which can suitably produce water resistant paper by using it for paper making. Further, according to the present invention, it is also possible to provide a method for producing a water resistant paper using a water resistant agent kit for papermaking and a water resistant paper.
本発明の抄紙用耐水剤キットは、少なくとも、カチオン性高分子凝結剤からなる第１剤と、非フッ素系耐水剤からなる第２剤とを備え、用時に紙料と、第１剤、第２剤を順次混合して、紙料が抄紙された紙基材に耐水性を付与するために用いられるものであることを特徴としている。本発明の抄紙用耐水剤キットは、このような構成を備えることにより、紙基材に対して耐水性を好適に付与することができる。 The water resistant kit for papermaking of the present invention includes at least a first agent made of a cationic polymer coagulant and a second agent made of a non-fluorine-based water resistant agent. The two agents are sequentially mixed, and the paper material is used to impart water resistance to the paper base material from which the paper has been made. By providing such a structure, the water resistant agent kit for papermaking of the present invention can suitably impart water resistance to a paper substrate.
また、本発明の耐水紙は、本発明の抄紙用耐水剤キットを利用して好適に製造することができる。すなわち、本発明の耐水紙は、本発明の抄紙用耐水剤キットを用いて、紙基材が耐水処理されてなる、耐水紙であることを特徴としている。本発明の耐水紙においては、少なくとも、カチオン性高分子凝結剤及び非フッ素系耐水剤が、紙基材に含まれている。本発明の耐水紙は、このような構成を備えることにより、優れた耐水性を発揮し得る。 Further, the water resistant paper of the present invention can be suitably produced by using the water resistant agent kit for papermaking of the present invention. That is, the water resistant paper of the present invention is characterized in that the paper base material is water resistant using the water resistant agent kit for papermaking of the present invention. In the water-resistant paper of the present invention, at least a cationic polymer coagulant and a non-fluorine-based water-resistant agent are contained in the paper base material. The water resistant paper of the present invention can exhibit excellent water resistance by providing such a structure.
また、本発明の耐水紙の製造方法は、発明の抄紙用耐水剤キットを利用した耐水紙の製造方法であり、少なくとも、カチオン性高分子凝結剤からなる第１剤を紙料と混合する工程１と、工程１で得られた混合物と、非フッ素系耐水剤からなる第２剤とを混合する工程２と、工程２で得られた混合物を抄紙する工程３とを備えることを特徴としている。本発明の耐水紙の製造方法は、このような構成を備えることにより、耐水紙を好適に製造することができる。 Further, the method for producing water-resistant paper of the present invention is a method for producing water-resistant paper using the water-resistant agent kit for papermaking of the present invention, and at least a step of mixing a first agent composed of a cationic polymer coagulant with a paper material. 1. It is characterized by comprising a step 2 of mixing the mixture obtained in step 1 and a second agent made of a non-fluorinated water resistant agent, and a step 3 of making a paper of the mixture obtained in step 2. .. The method for producing a water resistant paper of the present invention can suitably produce a water resistant paper by providing such a configuration.
以下、本発明の抄紙用耐水剤キット、耐水紙、及び耐水紙の製造方法について詳述する。 Hereinafter, the water resistant agent kit for papermaking, the water resistant paper, and the method for producing the water resistant paper of the present invention will be described in detail.
なお、本発明において、「電荷密度」とは、電荷量がゼロになるまで試料と反対の電荷をもった標準滴定液を試料に加えて求められる値である。一般的に、アニオン滴定液としてはポリエチレンスルホン酸ナトリウム（ＰＥＳ−Ｎａ）またはポリビニル硫酸カリウム（ＰＶＳＫ）が使用され、カチオン滴定液としてはポリジアリルジメチルアンモニウムクロライド（ＰｏｌｙＤＡＤＭＡＣ）が使用される。 In the present invention, the "charge density" is a value obtained by adding a standard titrant having a charge opposite to that of the sample until the amount of charge becomes zero. Generally, sodium polyethylene sulfonate (PES-Na) or potassium polyvinyl sulfate (PVSK) is used as the anion titration solution, and polydialyldimethylammonium chloride (PolyDADMAC) is used as the cation titration solution.
また、「紙料スラリー」とは、紙料が液状媒体に分散したものを意味し、例えば「パルプスラリー」とは、パルプが液状媒体に分散したものを意味する。 Further, the "paper slurry" means a paper material dispersed in a liquid medium, and for example, a "pulp slurry" means a pulp dispersed in a liquid medium.
また、「アニオン性基」とは、カチオンが解離したときに負電荷を有するようになる基を意味し、カチオンがプロトンである酸型と、カチオンがアルカリ金属イオン、アンモニウムイオン等である塩型とがある。 The "anionic group" means a group that has a negative charge when the cation is dissociated, and is an acid type in which the cation is a proton and a salt type in which the cation is an alkali metal ion, an ammonium ion, or the like. There is.
また、「（メタ）アクリレート」は、アクリレートおよびメタクリレートの総称である。 Further, "(meth) acrylate" is a general term for acrylate and methacrylate.
また、「主成分とする」とは、該成分を５０質量％以上含むことを意味する。 Further, "as a main component" means that the component is contained in an amount of 50% by mass or more.
［抄紙用耐水剤キット］
本発明の抄紙用耐水剤キットは、第１剤としてのカチオン性高分子凝結剤と、第２剤としての非フッ素系耐水剤とを備えている。本発明の抄紙用耐水剤キットは、次のようにして使用される。すなわち、後述する紙料と、第１剤としてのカチオン性高分子凝結剤とを混合して混合物を得る。次に、得られた混合物と、第２剤としての非フッ素系耐水剤とを混合して混合物を得る。このようにして得られたこの混合物を抄紙に供することにより、紙基材に非フッ素系耐水剤が好適に付着した紙基材が得られ、紙基材に対して耐水性が付与される。
[Water resistant kit for papermaking]
The water resistant kit for papermaking of the present invention includes a cationic polymer coagulant as a first agent and a non-fluorine water resistant agent as a second agent. The water resistant kit for papermaking of the present invention is used as follows. That is, a paper material described later and a cationic polymer coagulant as the first agent are mixed to obtain a mixture. Next, the obtained mixture is mixed with a non-fluorine-based water resistant agent as a second agent to obtain a mixture. By applying this mixture thus obtained to papermaking, a paper base material to which a non-fluorine-based water resistant agent is suitably attached to the paper base material is obtained, and water resistance is imparted to the paper base material.
（カチオン性高分子凝結剤）
カチオン性高分子凝結剤としては、通常の抄紙において用いられるカチオン性紙力増強剤等が挙げられる。カチオン性高分子凝結剤は、１種類のみを用いてもよいし、２種類以上を混合して用いてもよい。
(Cationic polymer coagulant)
Examples of the cationic polymer coagulant include a cationic paper strength enhancer used in ordinary papermaking. Only one type of cationic polymer coagulant may be used, or two or more types may be mixed and used.
カチオン性高分子凝結剤のカチオン電荷密度は、好ましくは＋１００．０〜＋１００００．０μｅｑ／ｇ程度である。カチオン性高分子凝結剤のカチオン電荷密度が前記範囲の下限値以上であれば、例えば古紙含有率の高い紙料（例えば、古紙含有率が６０％以上の紙料）のように、微細繊維を多く含む紙料を用いた場合にも、アニオン性の紙料（すなわち、セルロースなど）を好適にカチオン化することができる。また、カチオン性高分子凝結剤のカチオン電荷密度が前記範囲の上限値以下であれば、例えば古紙含有率の高い紙料のように、微細繊維を多く含む紙料を用いた場合にも、抄紙の際に、カチオン性高分子凝結剤によって微細繊維を好適に捕捉することができる。また、これらのカチオン電荷密度を満たすことにより、後述する非フッ素系耐水剤が、アニオン性（アニオン性非フッ素系耐水剤）であっても、カチオン性（すなわちカチオン性非フッ素系耐水剤）であっても、非フッ素系耐水剤が紙料表面に均一性高く定着することができる。 The cationic charge density of the cationic polymer coagulant is preferably about +100.0 to +10000.0 μeq / g. When the cationic charge density of the cationic polymer coagulant is equal to or higher than the lower limit of the above range, fine fibers are used, for example, a paper material having a high waste paper content (for example, a paper material having a waste paper content of 60% or more). Even when a paper material containing a large amount is used, an anionic paper material (that is, cellulose or the like) can be suitably cationized. Further, if the cationic charge density of the cationic polymer coagulant is not more than the upper limit of the above range, even when a paper material containing a large amount of fine fibers is used, for example, a paper material having a high waste paper content, papermaking is performed. At this time, the fine fibers can be suitably captured by the cationic polymer coagulant. Further, by satisfying these cationic charge densities, even if the non-fluorine-based water resistant agent described later is anionic (anionic non-fluorine-based water resistant agent), it is cationic (that is, cationic non-fluorine-based water resistant agent). Even if there is, the non-fluorine-based water resistant agent can be fixed on the surface of the paper material with high uniformity.
カチオン性高分子凝結剤の具体例としては、ポリアミンエピクロロヒドリン樹脂、ポリアミドエピクロロヒドリン樹脂、カチオン化澱粉、カチオン性ポリアクリルアミド〔アクリルアミド−アリルアミン共重合体、アクリルアミド−ジメチルアミノエチル（メタ）アクリレート共重合体、アクリルアミド−ジエチルアミノエチル（メタ）アクリレート共重合体、アクリルアミド−４級化ジメチルアミノエチル（メタ）アクリレート共重合体、アクリルアミド−４級化ジエチルアミノエチル（メタ）アクリレート共重合体など〕、カチオン変性ポリビニルアルコール、ポリジアリルジメチルアンモニウムクロライド又はその誘導体、ジアリルジメチルアンモニウムクロライドと他のモノマーの共重合体、ポリアミン、ポリアリルアミン、ポリビニルアミン、ポリエチレンイミン、２−（メタクリロイルオキシ）エチルトリメチルアンモニウムクロリド重合物、Ｎ−ビニルホルムアミド−ビニルアミン共重合体、メラミン樹脂、ポリアミドエポキシ樹脂、ポリアミドポリアミン樹脂、ジメチルアミンエピクロルヒドリン樹脂、ジメチルアミン−エチレンジアミンエピクロルヒドリン共重合体樹脂等が挙げられる。 Specific examples of the cationic polymer coagulant include polyamine epichlorohydrin resin, polyamide epichlorohydrin resin, cationized starch, and cationic polyacrylamide [acrylamide-allylamine copolymer, acrylamide-dimethylaminoethyl (meth)). Acrylic copolymer, acrylamide-diethylaminoethyl (meth) acrylate copolymer, acrylamide-4 grade dimethylaminoethyl (meth) acrylate copolymer, acrylamide-4 grade diethylaminoethyl (meth) acrylate copolymer, etc.], Cationic-modified polyvinyl alcohol, polydiallyldimethylammonium chloride or a derivative thereof, copolymer of diallyldimethylammonium chloride and other monomers, polyamine, polyallylamine, polyvinylamine, polyethyleneimine, 2- (methacryloyloxy) ethyltrimethylammonium chloride polymer , N-vinylformamide-vinylamine copolymer, melamine resin, polyamide epoxy resin, polyamide polyamine resin, dimethylamine epichlorohydrin resin, dimethylamine-ethylenediamine epichlorohydrin copolymer resin and the like.
紙料（固形分）１００．０質量部に対して、カチオン性高分子凝結剤の使用割合としては、好ましくは０．０５〜１０．０質量部程度、より好ましくは０．１〜５．０質量部程度である。 The ratio of the cationic polymer coagulant to 100.0 parts by mass of the paper material (solid content) is preferably about 0.05 to 10.0 parts by mass, more preferably 0.1 to 5.0 parts by mass. It is about a mass part.
また、本発明の抄紙用耐水剤キットにおいて、第１剤としてのカチオン性高分子凝結剤と、第２剤としての非フッ素系耐水剤との割合（第１剤：第２剤（質量比））としては、好ましくは１：０．５〜１００程度、より好ましくは１：１〜５０程度が挙げられる。 Further, in the water resistant agent kit for papermaking of the present invention, the ratio of the cationic polymer coagulant as the first agent and the non-fluorine-based water resistant agent as the second agent (first agent: second agent (mass ratio)). ) Is preferably about 1: 0.5 to 100, and more preferably about 1: 1 to 50.
（非フッ素系耐水剤）
本フッ素系耐水剤としては、アニオン性非フッ素系耐水剤、カチオン性非フッ素系耐水剤のいずれも使用可能であるが、紙料への非フッ素耐水剤の定着効率の観点からは、カチオン性非フッ素系耐水剤が好ましい。非フッ素系耐水剤は、１種類のみを用いてもよいし、２種類以上を混合して用いてもよい。
(Non-fluorine water resistant agent)
As this fluorine-based water resistant agent, either an anionic non-fluorine-based water resistant agent or a cationic non-fluorine-based water resistant agent can be used, but from the viewpoint of the fixing efficiency of the non-fluorine water resistant agent on paper materials, it is cationic. A non-fluorine-based water resistant agent is preferable. Only one type of non-fluorine-based water resistant agent may be used, or two or more types may be mixed and used.
非フッ素系耐水剤の具体例としては、長鎖アクリレート系耐水剤、長鎖アクリレート−シリコーンマクロモノマー共重合体系耐水剤、ハイブリッドエマルション系耐水剤、長鎖アクリレート−ハロゲン化オレフィン共重合体系耐水剤、長鎖アクリレート共重合体と長鎖アルキル変性シリコーン重合体のブレンド系耐水剤、長鎖アクリレート共重合体と塩化ビニル系重合体とシリコーン樹脂のブレンド系耐水剤、アミノ変性シリコーンとシリコーン樹脂と多官能イソシアネートのブレンド系耐水剤、ポリウレタン系耐水剤、ポリ尿素系耐水剤、ポリウレタンデンドリマー系耐水剤が挙げられる。 Specific examples of the non-fluorine-based water resistant agent include a long-chain acrylate-based water resistant agent, a long-chain acrylate-silicone macromonomer copolymer-based water resistant agent, a hybrid emulsion-based water resistant agent, and a long-chain acrylate-halogenated olefin copolymer-based water resistant agent. Blend-based water resistant agent of long-chain acrylate copolymer and long-chain alkyl-modified silicone polymer, blend-based water resistant agent of long-chain acrylate copolymer, vinyl chloride-based polymer and silicone resin, amino-modified silicone and silicone resin and polyfunctional Examples thereof include a blend type water resistant agent of isocyanate, a polyurethane type water resistant agent, a polyurea type water resistant agent, and a polyurethane dendrimer type water resistant agent.
非フッ素系耐水剤の電荷密度は、好ましくは−１００．０〜＋２００．０μｅｑ／ｇ程度である。 The charge density of the non-fluorine-based water resistant agent is preferably about -100.0 to +200.0 μeq / g.
（紙料）
本発明の抄紙用耐水剤キットが処理対象とする紙料としては、製紙に供されるものであれば特に制限されず、たとえば、非塗工紙の紙料が挙げられる。紙料としては、一般にパルプが使用される。パルプとしては、植物セルロースを含むもの（木材、草、竹、稲わら、葦、バガス、ヤシ等）が挙げられる。また、古紙を処理して製造されるリサイクルパルプを用いてもよい。パルプは、１種類のみを用いてもよいし、２種類以上を混合して用いてもよい。
(Paper charge)
The paper material to be treated by the water resistant agent kit for papermaking of the present invention is not particularly limited as long as it is used for papermaking, and examples thereof include a paper material for uncoated paper. Pulp is generally used as the paper material. Examples of the pulp include those containing plant cellulose (wood, grass, bamboo, rice straw, reeds, bagasse, palm, etc.). Further, recycled pulp produced by processing used paper may be used. Only one type of pulp may be used, or two or more types may be mixed and used.
パルプの具体例としては、針葉樹の晒しクラフトパルプ（ＮＢＫＰ）、広葉樹の晒しクラフトパルプ（ＬＢＫＰ）、砕木パルプ（ＧＰ）、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）、脱墨パルプ（ＤＩＰ）等が挙げられる。また、本発明の抄紙用耐水剤は、前記の通り、古紙含有率の高いパルプ（例えば、古紙含有率が６０％以上のパルプ）を使用して紙を製造する場合に、特に好適である。本発明に用いられる古紙パルプとしては、例えば、茶古紙、クラフト封筒古紙、雑誌古紙、新聞古紙、チラシ古紙、オフィス古紙、段ボール古紙、上白古紙、ケント古紙、模造古紙、地券古紙等から製造される離解古紙パルプ、離解・脱墨古紙パルプ（ＤＩＰ）又は離解・脱墨・漂白古紙パルプ等が挙げられる。 Specific examples of pulp include softwood bleached kraft pulp (NBKP), broadleaf bleached kraft pulp (LBKP), crushed wood pulp (GP), thermomechanical pulp (TMP), chemithermomechanical pulp (CTMP), and deinked pulp (inking pulp). DIP) and the like. Further, as described above, the water resistant agent for papermaking of the present invention is particularly suitable when paper is produced using pulp having a high waste paper content (for example, pulp having a waste paper content of 60% or more). The used paper pulp used in the present invention is manufactured from, for example, tea waste paper, craft envelope waste paper, magazine waste paper, newspaper waste paper, leaflet waste paper, office waste paper, cardboard waste paper, upper white waste paper, Kent waste paper, imitation waste paper, ground ticket waste paper and the like. Examples thereof include disintegrated recycled paper pulp, disaggregated / deinked recycled paper pulp (DIP), and disaggregated / deinked / bleached recycled paper pulp.
本発明の抄紙用耐水剤キットは、抄紙の工程で使用することが好適である。従って、紙料はスラリー（好ましくはパルプスラリー）の状態で、本発明の抄紙用耐水剤キットの第１剤、第２剤と順次混合されることが好ましい。一般に、製紙における抄紙工程では、紙料を水に分散させて希釈した後、得られた紙料のスラリーをワイヤー（網）に載せて水を落とすことで抄紙されている（ワイヤーパート）。本発明の抄紙用耐水剤キットは、抄紙工程において、第１剤（カチオン性高分子凝結剤）を紙料スラリーに添加することにより、紙料に第１剤が好適に付着し、さらに第１剤が紙料に付着することにより、第２剤（非フッ素系耐水剤）も紙料に好適に付着するため、ワイヤーパートでの非フッ素系耐水剤の流出が抑制され、抄紙後の紙基材に対して、好適に耐水性を付与することができる。このような耐水性の付与は、微細繊維を多く含む、古紙含有率の高いパルプを紙料とする場合に、特に顕著な効果を発現することができる。本発明においては、カチオン性高分子凝結剤のカチオン電荷密度が前記の範囲にある場合、当該効果を奏するために特に有効である。 The water resistant kit for papermaking of the present invention is preferably used in the papermaking process. Therefore, it is preferable that the paper material is sequentially mixed with the first agent and the second agent of the water resistant agent kit for papermaking of the present invention in the state of a slurry (preferably pulp slurry). Generally, in the papermaking process in papermaking, paper is made by dispersing the paper material in water, diluting it, and then placing the obtained slurry of the paper material on a wire (net) to remove water (wire part). In the water resistant kit for papermaking of the present invention, by adding the first agent (cationic polymer coagulant) to the paper material slurry in the papermaking process, the first agent is suitably adhered to the paper material, and further, the first agent When the agent adheres to the paper material, the second agent (non-fluorine-based water resistant agent) also adheres suitably to the paper material, so that the outflow of the non-fluorine-based water resistant agent at the wire part is suppressed, and the paper base after papermaking. Water resistance can be suitably imparted to the material. Such imparting of water resistance can exhibit a particularly remarkable effect when pulp containing a large amount of fine fibers and having a high content of used paper is used as a paper material. In the present invention, when the cationic charge density of the cationic polymer coagulant is in the above range, it is particularly effective to exert the effect.
本発明の抄紙用耐水剤キットを利用する抄紙工程においては、第１剤及び第２剤に加えて、さらに他の添加剤を加えてもよい。添加剤としては、公知の紙の製造方法の抄紙工程で使用されているものを使用することができ、例えば、柔軟剤、サイズ剤、定着剤、乾燥紙力剤、湿潤紙力剤、硫酸バンド、歩留り向上剤、染料、顔料等が挙げられる。例えば、サイズ剤としては、カチオン性サイズ剤、アニオン性サイズ剤、ロジン系サイズ剤（例えば、酸性ロジン系サイズ剤、中性ロジン系サイズ剤等）、スチレン−アクリル酸系共重合体、アルケニルコハク酸無水物、アルキルケテンダイマー等が挙げられる。
添加剤の使用量は、適宜調整すればよく、例えば、サイズ剤の量は、紙料（固形分）１００質量部に対して０．００１〜５．０質量部程度とすることができる。
In the papermaking process using the water resistant agent kit for papermaking of the present invention, other additives may be added in addition to the first agent and the second agent. As the additive, those used in the papermaking process of a known paper manufacturing method can be used, for example, a softener, a sizing agent, a fixing agent, a dry paper strength agent, a wet paper strength agent, and a sulfate band. , Yield improver, dye, pigment and the like. For example, examples of sizing agents include cationic sizing agents, anionic sizing agents, rosin-based sizing agents (for example, acidic rosin-based sizing agents, neutral rosin-based sizing agents, etc.), styrene-acrylic acid-based copolymers, and alkenyl shavings. Acid anhydride, alkyl keten dimer and the like can be mentioned.
The amount of the additive used may be appropriately adjusted. For example, the amount of the sizing agent can be about 0.001 to 5.0 parts by mass with respect to 100 parts by mass of the paper material (solid content).
［耐水紙の製造方法］
本発明の耐水紙の製造方法は、カチオン性高分子凝結剤からなる第１剤を紙料と混合する工程１と、工程１で得られた混合物と、非フッ素系耐水剤からなる第２剤とを混合する工程２と、工程２で得られた混合物を抄紙する工程３とを備える。
[Manufacturing method of waterproof paper]
The method for producing water-resistant paper of the present invention is a step 1 of mixing a first agent made of a cationic polymer coagulant with a paper material, a second agent made of a mixture obtained in step 1 and a non-fluorine-based water-resistant agent. A step 2 in which the above is mixed and a step 3 in which the mixture obtained in the step 2 is made into paper are provided.
本発明の耐水紙の製造方法は、例えば、前述した本発明の抄紙用耐水剤キットを用いることにより、好適に製造することができる。 The method for producing a water resistant paper of the present invention can be suitably produced by using, for example, the above-mentioned water resistant agent kit for papermaking of the present invention.
工程１においては、カチオン性高分子凝結剤からなる第１剤を紙料と混合する。カチオン性高分子凝結剤、紙料の詳細については、前述の通りである。 In step 1, the first agent composed of a cationic polymer coagulant is mixed with the paper material. Details of the cationic polymer coagulant and the paper material are as described above.
なお、紙料としてパルプを用いる場合、植物セルロースなどのパルプ化法としては、機械パルプ化法、サーモメカニカルパルプ化法、ケミサーモメカニカルパルプ化法、クラフトパルプ化法、サルファイトパルプ化法、脱墨パルプ化法、リサイクルパルプ化法等、公知のパルプ化法を採用できる。 When pulp is used as a paper material, the pulping methods for plant cellulose and the like include mechanical pulping method, thermomechanical pulping method, chemithermomechanical pulping method, kraft pulping method, sulfite pulping method, and desorption. Known pulping methods such as the ink pulping method and the recycled pulping method can be adopted.
前記の通り、紙料は水に分散したスラリー状とし、当該スラリーに対して、第１剤を添加、混合することが好ましい。紙料のスラリーは、紙料を液状媒体に公知の方法によって離解することによって調製できる。離解方法としては、ディスインテグレータを用いる方法等が挙げられる。液状媒体としては、水を主成分とする水性媒体が好ましい。水性媒体としては、取り扱い性および安全衛生の点から、水、または水と、水と共沸混合物を形成する有機溶媒とを含む共沸混合物が好ましい。該有機溶媒としては、プロピレングリコール、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコール、トリプロピレングリコール、ダイアセトンアルコール等が挙げられる。 As described above, it is preferable that the paper material is in the form of a slurry dispersed in water, and the first agent is added and mixed with the slurry. The paper material slurry can be prepared by separating the paper material into a liquid medium by a known method. Examples of the dissociation method include a method using a disintegrator. As the liquid medium, an aqueous medium containing water as a main component is preferable. As the aqueous medium, water or an azeotropic mixture containing water and an organic solvent that forms an azeotropic mixture with water is preferable from the viewpoint of handleability and safety and health. Examples of the organic solvent include propylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol, tripropylene glycol, diacetone alcohol and the like.
スラリー中の紙料の濃度の下限は、０．３質量％が好ましく、０．７質量％がより好ましく、１．０質量％がさらに好ましい。スラリー中の紙料の濃度の上限は、６．０質量％が好ましく、５．０質量％がより好ましく、４．０質量％がさらに好ましい。紙料の濃度が前記範囲の下限値以上であれば、本発明の効果が充分に発揮される。紙料の濃度が前記範囲の上限値以下であれば、微細繊維がさらに凝集しにくい。そのため、カチオン性高分子凝結剤によって微細繊維の表面をさらに均一にカチオン化できる。 The lower limit of the concentration of the paper material in the slurry is preferably 0.3% by mass, more preferably 0.7% by mass, and even more preferably 1.0% by mass. The upper limit of the concentration of the paper material in the slurry is preferably 6.0% by mass, more preferably 5.0% by mass, still more preferably 4.0% by mass. When the concentration of the paper material is equal to or higher than the lower limit of the above range, the effect of the present invention is fully exhibited. When the concentration of the paper material is not more than the upper limit of the above range, the fine fibers are less likely to aggregate. Therefore, the surface of the fine fibers can be more uniformly cationized by the cationic polymer coagulant.
工程１において、カチオン性高分子凝結剤の混合割合は、紙料（固形分１００．０質量部）に対して０．３〜５．０質量部が好ましく、１．０〜４．０質量部がより好ましい。カチオン性高分子凝結剤の混合割合が前記範囲の下限値以上であれば、カチオン性高分子凝結剤によって微細繊維をさらに充分にカチオン化することができる。カチオン性高分子凝結剤の混合割合が前記範囲の上限値以下であれば、例えばスラリー中の古紙含有率が高くなっても、カチオン性高分子凝結剤によって紙料がさらに凝集しにくい。そのため、カチオン性高分子凝結剤によって微細繊維をさらに均一にカチオン化することができる。 In step 1, the mixing ratio of the cationic polymer coagulant is preferably 0.3 to 5.0 parts by mass, and 1.0 to 4.0 parts by mass with respect to the paper material (solid content 100.0 parts by mass). Is more preferable. When the mixing ratio of the cationic polymer coagulant is equal to or higher than the lower limit of the above range, the fine fibers can be more sufficiently cationized by the cationic polymer coagulant. When the mixing ratio of the cationic polymer coagulant is not more than the upper limit of the above range, for example, even if the content of used paper in the slurry is high, the paper material is less likely to be aggregated by the cationic polymer coagulant. Therefore, the fine fibers can be more uniformly cationized by the cationic polymer coagulant.
工程２においては、工程１で得られた紙料及び第１剤の混合物と、非フッ素系耐水剤からなる第２剤とを混合する。非フッ素系耐水剤の詳細については、前述の通りである。前記の通り、紙料は水に分散したスラリー状とし、当該スラリーに対して、工程１で第１剤を添加、混合し、さらに工程２で第２剤を添加することが好ましい。 In step 2, the mixture of the paper material and the first agent obtained in step 1 and the second agent made of a non-fluorine-based water resistant agent are mixed. Details of the non-fluorine-based water resistant agent are as described above. As described above, it is preferable that the paper material is in the form of a slurry dispersed in water, the first agent is added and mixed in step 1 and the second agent is further added in step 2.
工程２において、非フッ素系耐水剤の混合割合は、紙料（固形分１００．０質量部）に対して０．５〜２０．０質量部が好ましく、１．０〜１５．０質量部がより好ましく、１．０〜１０．０質量部が特に好ましい。非フッ素系耐油剤の混合割合が前記範囲の下限値以上であれば、耐水性にさらに優れる耐水紙が得られる。非フッ素系耐油剤の含有割合が前記範囲の上限値以下であれば、コスト面で有利である。 In step 2, the mixing ratio of the non-fluorine-based water resistant agent is preferably 0.5 to 20.0 parts by mass, and 1.0 to 15.0 parts by mass with respect to the paper material (solid content 100.0 parts by mass). More preferably, 1.0 to 10.0 parts by mass is particularly preferable. When the mixing ratio of the non-fluorine-based oil resistant agent is at least the lower limit of the above range, a water resistant paper having further excellent water resistance can be obtained. If the content ratio of the non-fluorine-based oil resistant agent is not more than the upper limit of the above range, it is advantageous in terms of cost.
なお、工程１及び工程２においては、それぞれ、本発明の効果を損なわない範囲内で前述した添加剤を混合することができる。また、第１剤、第２剤、必要に応じて混合される前記の添加剤の混合は、後述する工程３の抄紙において、紙料をワイヤ上に供給する前であれば、どの段階で行ってもよく、具体的には、パルプ製造工程、紙料調製工程等で行うことができ、紙料調製工程で行うことが好ましい。 In each of Step 1 and Step 2, the above-mentioned additives can be mixed within a range that does not impair the effects of the present invention. Further, the first agent, the second agent, and the above-mentioned additive to be mixed as needed are mixed at any stage in the papermaking of step 3 described later, as long as the paper material is not supplied on the wire. Specifically, it can be carried out in a pulp manufacturing step, a paper material preparation step, or the like, and is preferably carried out in a paper material preparation step.
工程３においては、工程２で得られた混合物を抄紙する。抄紙方法は、製紙において採用されている公知の抄紙方法を採用することができ、一般には、抄紙機を用いて実施される。抄紙機は、紙料スラリーをワイヤ上で脱水可能な装置であればよい。抄紙機としては、長網抄紙機のような連続式の抄紙機のほかに、紙料スラリーをワイヤで形成された成型枠上に添加した後に、ワイヤ下部から脱水し、成型体を製造する、バッチ式のモールド成型機等もその範疇に含める。 In step 3, the mixture obtained in step 2 is made into paper. As the papermaking method, a known papermaking method used in papermaking can be adopted, and it is generally carried out using a paper machine. The paper machine may be any device capable of dehydrating the paper slurry on the wire. As a paper machine, in addition to a continuous paper machine such as a long net paper machine, a paper material slurry is added onto a molding frame formed of a wire and then dehydrated from the lower part of the wire to produce a molded product. Batch type molding machines are also included in this category.
本発明の耐水紙の製造方法によれば、以上のように、カチオン性高分子凝結剤及び非フッ素系耐水剤が紙基材の全体に分散した耐水紙が製造される。すなわち、本発明の耐水紙の全体にカチオン性高分子凝結剤及び非フッ素系耐水剤が含まれることから、例えば紙基材の表面部分にのみ耐水性が付与された耐水紙と比較すると、耐水紙の折り目、皺による耐水性低下を好適に抑制することができる。 According to the method for producing a water-resistant paper of the present invention, as described above, a water-resistant paper in which the cationic polymer coagulant and the non-fluorine-based water-resistant agent are dispersed throughout the paper base material is produced. That is, since the water-resistant paper of the present invention contains a cationic polymer coagulant and a non-fluorine-based water-resistant agent, it is water-resistant as compared with, for example, a water-resistant paper in which water resistance is imparted only to the surface portion of the paper base material. Deterioration of water resistance due to creases and wrinkles of paper can be suitably suppressed.
［耐水紙］
本発明の耐水紙は、少なくとも、紙基材と、カチオン性高分子凝結剤と、非フッ素系耐水剤とを含む。前記の通り、本発明の耐水紙は、カチオン性高分子凝結剤及び非フッ素系耐水剤が、紙基材の全体に分散された耐水紙とすることができる。
[Water resistant paper]
The water-resistant paper of the present invention contains at least a paper base material, a cationic polymer coagulant, and a non-fluorine-based water-resistant agent. As described above, the water-resistant paper of the present invention can be a water-resistant paper in which a cationic polymer coagulant and a non-fluorine-based water resistant agent are dispersed throughout the paper substrate.
本発明の耐水紙の製造方法は、特に限定されないが、例えば、前述の本発明の抄紙用耐水剤キットを用いて、紙基材を耐水処理することで好適に製造される。具体的には、前述の本発明の製造方法を採用することで好適に製造される。 The method for producing the water resistant paper of the present invention is not particularly limited, but for example, it is suitably produced by treating the paper base material with water resistance using the above-mentioned water resistant agent kit for papermaking of the present invention. Specifically, it is suitably manufactured by adopting the above-mentioned manufacturing method of the present invention.
耐水紙に含まれるカチオン性高分子凝結剤、非フッ素系耐水剤、紙料、必要に応じて混合される添加剤等については、前記の通りである。 The cationic polymer coagulant, non-fluorine-based water resistant agent, paper material, additives to be mixed as necessary, etc. contained in the water resistant paper are as described above.
本発明の耐水紙において、カチオン性高分子凝結剤の含有割合は、好ましくは０．０５〜１０．０質量％であり、より好ましくは０．１〜５．０質量％である。また、非フッ素系耐水剤の含有割合は、好ましくは０．５〜２０．０質量％であり、より好ましくは１.０〜１５．０質量％であり、特に好ましくは１．０〜１０．０質量％である。また、本発明の耐水紙において、カチオン性高分子凝結剤及び非フッ素系耐水剤の合計含有量は、好ましくは０．０５〜１０．０ｇ／ｍ2、より好ましくは０．１〜５．０ｇ／ｍ2である。 In the water-resistant paper of the present invention, the content ratio of the cationic polymer coagulant is preferably 0.05 to 10.0% by mass, more preferably 0.1 to 5.0% by mass. The content of the non-fluorine-based water resistant agent is preferably 0.5 to 20.0% by mass, more preferably 1.0 to 15.0% by mass, and particularly preferably 1.0 to 15.0% by mass. It is 0% by mass. Further, in the water resistant paper of the present invention, the total content of the cationic polymer coagulant and the non-fluorine water resistant agent is preferably 0.05 to 10.0 g / m 2 , more preferably 0.1 to 5.0 g. / M 2 .
また、本発明の耐水紙は、ＪＩＳ Ｐ８１４０：１９９８（紙及び板紙−吸水度試験方法−コッブ法）の規定に準拠して測定されるコブ吸水度が、２５．０ｇ／ｍ2以下であることが好ましく、２１．０ｇ／ｍ2以下であることがより好ましい。 Further, the water-resistant paper of the present invention has a bump water absorption of 25.0 g / m 2 or less measured in accordance with the provisions of JIS P8140: 1998 (paper and paperboard-water absorption test method-cobb method). Is preferable, and it is more preferably 21.0 g / m 2 or less.
本発明の耐水紙において、紙基材の形態としては、長尺のウェブ状のもの、これを裁断した枚葉状のもの、パルプモールド成型機で得られた成型体（容器等）等が挙げられる。 In the water-resistant paper of the present invention, examples of the form of the paper base material include a long web-like one, a single-wafer-shaped one obtained by cutting the paper base material, and a molded body (container, etc.) obtained by a pulp molding machine. ..
本発明の耐水紙において、紙基材の表面には、紙基材とは異なる他の層が設けられていてもよい。他の層としては、紙基材の表面に顔料を含む塗料を塗工して形成された、いわゆる塗工紙における塗工層等が挙げられる。 In the water resistant paper of the present invention, another layer different from the paper base material may be provided on the surface of the paper base material. Examples of the other layer include a coating layer on so-called coated paper, which is formed by applying a paint containing a pigment on the surface of a paper base material.
以下に実施例、比較例、及び参考例を示して本発明を詳細に説明する。但し本発明は実施例に限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to Examples, Comparative Examples, and Reference Examples. However, the present invention is not limited to the examples.
（電荷密度）
電荷密度の測定には、ＢＴＧ社の粒子電荷計（Ｐａｔｉｃｌｅ Ｃｈａｒｇｅ Ｄｅｔｅｃｔｏｒ ＰＣＤ０３）を用いた。滴定量が０．１〜１．０ｍｌとなるように測定試料を水で希釈し、メスピペットで測定容器に希釈した試料を１０．０ｍｌ測り取り、カチオン性試料の測定の際はアニオン滴定液を滴定、アニオン性試料の測定の際はカチオン滴定液で滴定し、その滴定量から電荷密度を計算した。
(Charge density)
A particle charge meter (Paticle Charge Detector PCD03) manufactured by BTG was used for the measurement of the charge density. Dilute the measurement sample with water so that the titration amount is 0.1 to 1.0 ml, measure 10.0 ml of the diluted sample in the measurement container with a measuring pipe, and use an anionic titration solution when measuring the cationic sample. When titrating and measuring anionic samples, titration was performed with a cation titration solution, and the charge density was calculated from the titration amount.
（カチオン性高分子凝結剤）
カチオン性高分子凝結剤として、以下のものを使用した。
・カチオン性高分子凝結剤（Ａ１）：ポリアミドエピクロロヒドリン、Ｈｅｒｃｕｌｅｓ社製Ｋｙｍｅｎｅ ５５７Ｈ、電荷密度２０１０μｅｑ／１ｇ（固形分）
・カチオン性高分子凝結剤（Ａ２）：カチオン性ポリアクリルアミド、明成化学社製アロマフィックスＰＴ、電荷密度５５０μｅｑ／１ｇ（固形分）
・カチオン性高分子凝結剤（Ａ３）：ポリジアリルジメチルアンモニウムクロライド、明成化学社製ＡＧフィックス Ｍ−８０、電荷密度６２００μｅｑ／１ｇ（固形分）
(Cationic polymer coagulant)
The following were used as the cationic polymer coagulant.
Cationic polymer coagulant (A1): Polyamide epichlorohydrin, Hercules Kymene 557H, charge density 2010 μeq / 1 g (solid content)
Cationic polymer coagulant (A2): Cationic polyacrylamide, Aromafix PT manufactured by Meisei Kagaku Co., Ltd., charge density 550 μeq / 1 g (solid content)
Cationic polymer coagulant (A3): Polydiallyl dimethylammonium chloride, AG Fix M-80 manufactured by Meisei Kagaku Co., Ltd., charge density 6200 μeq / 1 g (solid content)
（非フッ素系耐水剤）
非フッ素系耐水剤として、以下のものを使用した。
・非フッ素系耐水剤（Ｂ１）：長鎖アクリレート−シリコーン共重合体系耐水剤、電荷密度８８．０μｅｑ／１ｇ（固形分）
・非フッ素系耐水剤（Ｂ２）：長鎖アクリレート−塩化ビニル共重合体系耐水剤、電荷密度１００．６μｅｑ／１ｇ（固形分）
・非フッ素系耐水剤（Ｂ３）：ハイブリッドエマルション系耐水剤、電荷密度５．２μｅｑ／１ｇ（固形分）
・非フッ素系耐水剤（Ｂ４）：長鎖アクリレート−シリコーン共重合体系耐水剤、電荷密度−５８．０μｅｑ／１ｇ（固形分）
・非フッ素系耐水剤（Ｂ５）：長鎖アクリレート系耐水剤、電荷密度−５６８．０μｅｑ／１ｇ（固形分）
(Non-fluorine water resistant agent)
The following were used as non-fluorine-based water resistant agents.
-Non-fluorine-based water resistant agent (B1): Long-chain acrylate-silicone copolymer system water resistant agent, charge density 88.0 μeq / 1 g (solid content)
-Non-fluorine-based water resistant agent (B2): Long-chain acrylate-vinyl chloride copolymer system water resistant agent, charge density 100.6 μeq / 1 g (solid content)
-Non-fluorine-based water resistant agent (B3): Hybrid emulsion-based water resistant agent, charge density 5.2 μeq / 1 g (solid content)
-Non-fluorine-based water resistant agent (B4): Long-chain acrylate-silicone copolymer system water resistant agent, charge density-58.0 μeq / 1 g (solid content)
-Non-fluorine-based water resistant agent (B5): Long-chain acrylate-based water resistant agent, charge density-568.0 μeq / 1 g (solid content)
（実施例１）
段ボール古紙パルプを水に分散させパルプ濃度を１質量％に調整し、薬剤未添加の段ボール古紙パルプスラリーを得た。薬剤未添加の段ボール古紙パルプスラリーに、カチオン性高分子凝結剤（Ａ１）をパルプスラリー中のパルプ１００．０質量部に対して０．２質量部となるように添加し、５分間攪拌した。さらに非フッ素系耐水剤（Ｂ１）をパルプスラリー中のパルプ１００．０質量部に対して５．４質量部となるように添加し、５分間攪拌した後、坪量が５０ｇ／ｍ2となるように抄紙し、本発明に係る耐水紙を得た。
(Example 1)
The corrugated cardboard waste paper pulp was dispersed in water to adjust the pulp concentration to 1% by mass to obtain a corrugated cardboard waste paper pulp slurry to which no chemical was added. A cationic polymer coagulant (A1) was added to 100.0 parts by mass of the pulp in the pulp slurry so as to be 0.2 parts by mass, and the mixture was stirred for 5 minutes. Further, a non-fluorine-based water resistant agent (B1) was added so as to be 5.4 parts by mass with respect to 100.0 parts by mass of the pulp in the pulp slurry, and after stirring for 5 minutes, the basis weight became 50 g / m 2. The paper was made in this manner to obtain a water resistant paper according to the present invention.
（実施例２）
カチオン性高分子凝結剤（Ａ１）の添加量をパルプスラリー中のパルプ１００．０質量部に対して３．６質量部に変更した以外は実施例１と同様にして耐水紙を得た。
(Example 2)
A water resistant paper was obtained in the same manner as in Example 1 except that the amount of the cationic polymer coagulant (A1) added was changed to 3.6 parts by mass with respect to 100.0 parts by mass of the pulp in the pulp slurry.
（実施例３）
カチオン性高分子凝結剤（Ａ１）をカチオン性高分子凝結剤（Ａ２）に変更した以外は実施例１と同様にして耐水紙を得た。
(Example 3)
A water resistant paper was obtained in the same manner as in Example 1 except that the cationic polymer coagulant (A1) was changed to the cationic polymer coagulant (A2).
（実施例４）
カチオン性高分子凝結剤（Ａ２）の添加量をパルプスラリー中のパルプ１００．０質量部に対して３．６質量部に変更した以外は実施例３と同様にして耐水紙を得た。
(Example 4)
A water resistant paper was obtained in the same manner as in Example 3 except that the amount of the cationic polymer coagulant (A2) added was changed to 3.6 parts by mass with respect to 100.0 parts by mass of the pulp in the pulp slurry.
（実施例５）
カチオン性高分子凝結剤（Ａ１）をカチオン性高分子凝結剤（Ａ３）に変更した以外は実施例１と同様にして耐水紙を得た。
(Example 5)
A water resistant paper was obtained in the same manner as in Example 1 except that the cationic polymer coagulant (A1) was changed to the cationic polymer coagulant (A3).
（実施例６）
非フッ素系耐水剤（Ｂ１）を非フッ素系耐水剤（Ｂ２）に変更した以外は実施例１と同様にして耐水紙を得た。
(Example 6)
A water resistant paper was obtained in the same manner as in Example 1 except that the non-fluorine water resistant agent (B1) was changed to the non-fluorine water resistant agent (B2).
（実施例７）
非フッ素系耐水剤（Ｂ１）を非フッ素系耐水剤（Ｂ３）に変更した以外は実施例１と同様にして耐水紙を得た。
(Example 7)
A water resistant paper was obtained in the same manner as in Example 1 except that the non-fluorine water resistant agent (B1) was changed to the non-fluorine water resistant agent (B3).
（実施例８）
非フッ素系耐水剤（Ｂ３）の添加量をパルプスラリー中のパルプ１００．０質量部に対して３．６質量部に変更した以外は実施例７と同様にして耐水紙を得た。
(Example 8)
A water resistant paper was obtained in the same manner as in Example 7 except that the amount of the non-fluorine-based water resistant agent (B3) added was changed to 3.6 parts by mass with respect to 100.0 parts by mass of the pulp in the pulp slurry.
（実施例９）
非フッ素系耐水剤（Ｂ３）の添加量をパルプスラリー中のパルプ１００．０質量部に対して７．２質量部に変更した以外は実施例７と同様にして耐水紙を得た。
(Example 9)
A water resistant paper was obtained in the same manner as in Example 7 except that the amount of the non-fluorine-based water resistant agent (B3) added was changed to 7.2 parts by mass with respect to 100.0 parts by mass of the pulp in the pulp slurry.
（実施例１０）
非フッ素系耐水剤（Ｂ１）を非フッ素系耐水剤（Ｂ４）に変更した以外は実施例１と同様にして耐水紙を得た。
(Example 10)
A water resistant paper was obtained in the same manner as in Example 1 except that the non-fluorine water resistant agent (B1) was changed to the non-fluorine water resistant agent (B4).
（実施例１１）
カチオン性高分子凝結剤（Ａ１）の添加量をパルプスラリー中のパルプ１００．０質量部に対して２．４質量部に変更した以外は実施例１０と同様にして耐水紙を得た。
(Example 11)
A water resistant paper was obtained in the same manner as in Example 10 except that the amount of the cationic polymer coagulant (A1) added was changed to 2.4 parts by mass with respect to 100.0 parts by mass of the pulp in the pulp slurry.
（実施例１２）
非フッ素系耐水剤（Ｂ４）の添加量をパルプスラリー中のパルプ１００．０質量部に対して３．６質量部に変更した以外は実施例１１と同様にして耐水紙を得た。
(Example 12)
A water resistant paper was obtained in the same manner as in Example 11 except that the amount of the non-fluorine-based water resistant agent (B4) added was changed to 3.6 parts by mass with respect to 100.0 parts by mass of the pulp in the pulp slurry.
（実施例１３）
カナダ標準フリーネスが１４０ｍｌとなるようにリファイナーで調整した広葉樹漂白クラフトパルプ（ＬＢＫＰ）と針葉樹漂白クラフトパルプ（ＮＢＫＰ）とを乾燥質量でＬＢＫＰ：ＮＢＫＰ＝７０：３０となるように混合し、水に分散させパルプ濃度を１質量％に調整し、薬剤未添加のバージンパルプスラリーを得た。
(Example 13)
Hardwood bleached kraft pulp (LBKP) adjusted with a refiner so that the Canadian standard freeness is 140 ml and softwood bleached kraft pulp (NBKP) are mixed in a dry mass so that LBKP: NBKP = 70: 30 and dispersed in water. The pulp concentration was adjusted to 1% by mass to obtain a chemical-free virgin pulp slurry.
薬剤未添加のバージンパルプスラリーに、カチオン性高分子凝結剤（Ａ１）をパルプスラリー中のパルプ１００．０質量部に対して０．２質量部となるように添加し、５分間攪拌した。さらに非フッ素系耐水剤（Ｂ１）をパルプスラリー中のパルプ１００質量部に対して５．４質量部となるように添加し、５分間攪拌した後、坪量が５０ｇ／ｍ2となるように抄紙し、耐水紙を得た。 To the virgin pulp slurry to which no chemical was added, the cationic polymer coagulant (A1) was added so as to be 0.2 parts by mass with respect to 100.0 parts by mass of the pulp in the pulp slurry, and the mixture was stirred for 5 minutes. Further, a non-fluorine-based water resistant agent (B1) was added so as to be 5.4 parts by mass with respect to 100 parts by mass of pulp in the pulp slurry, and after stirring for 5 minutes, the basis weight was 50 g / m 2. Paper was made to obtain water resistant paper.
（実施例１４）
非フッ素系耐水剤（Ｂ１）を非フッ素系耐水剤（Ｂ３）に変更し、さらに非フッ素系耐水剤の添加量をパルプスラリー中のパルプ１００．０質量部に対して１．８質量部に変更した以外は実施例１３と同様にして耐水紙を得た。
(Example 14)
The non-fluorine-based water resistant agent (B1) was changed to the non-fluorine-based water resistant agent (B3), and the amount of the non-fluorine-based water resistant agent added was increased to 1.8 parts by mass with respect to 100.0 parts by mass of the pulp in the pulp slurry. A water resistant paper was obtained in the same manner as in Example 13 except that it was changed.
（比較例１）
実施例１の耐水紙の製造においてカチオン性高分子凝結剤（Ａ１）を添加しなかった以外は実施例１と同様にして耐水紙を得た。
(Comparative Example 1)
A water resistant paper was obtained in the same manner as in Example 1 except that the cationic polymer coagulant (A1) was not added in the production of the water resistant paper of Example 1.
（比較例２）
実施例１の耐水紙の製造において非フッ素系耐水剤（Ｂ１）を添加しなかった以外は実施例１と同様にして耐水紙を得た。
(Comparative Example 2)
A water resistant paper was obtained in the same manner as in Example 1 except that the non-fluorine-based water resistant agent (B1) was not added in the production of the water resistant paper of Example 1.
（比較例３）
実施例１３の耐水紙の製造においてカチオン性高分子凝結剤（Ａ１）を添加しなかった以外は実施例１３と同様にして耐水紙を得た。
(Comparative Example 3)
A water resistant paper was obtained in the same manner as in Example 13 except that the cationic polymer coagulant (A1) was not added in the production of the water resistant paper of Example 13.
（比較例４）
実施例１３の耐水紙の製造において非フッ素系耐水剤（Ｂ１）を添加しなかった以外は実施例１３と同様にして耐水紙を得た。
(Comparative Example 4)
A water resistant paper was obtained in the same manner as in Example 13 except that the non-fluorine-based water resistant agent (B1) was not added in the production of the water resistant paper of Example 13.
（参考例１）
カチオン性高分子凝結剤（Ａ３）の添加量をパルプスラリー中のパルプ１００．０質量部に対して１．６質量部に変更した以外は実施例５と同様にして耐水紙を得た。
(Reference example 1)
A water resistant paper was obtained in the same manner as in Example 5 except that the amount of the cationic polymer coagulant (A3) added was changed to 1.6 parts by mass with respect to 100.0 parts by mass of the pulp in the pulp slurry.
（参考例２）
非フッ素系耐水剤（Ｂ１）を非フッ素系耐水剤（Ｂ５）に変更した以外は実施例１と同様にして耐水紙を得た。
(Reference example 2)
A water resistant paper was obtained in the same manner as in Example 1 except that the non-fluorine water resistant agent (B1) was changed to the non-fluorine water resistant agent (B5).
得られた耐水紙について、以下の評価を行った。その評価結果は表１に示す通りであった。 The obtained water resistant paper was evaluated as follows. The evaluation results are as shown in Table 1.
（吸水度）
ＪＩＳ Ｐ ８１４０：１９９８の「紙及び板紙−吸水度試験方法−コッブ法」に従い、接触時間：６０秒、試験時間：２２℃にて試験紙の吸水度を測定した。
(Water absorption)
According to JIS P 8140: 1998 "Paper and Paperboard-Water Absorption Test Method-Cobb Method", the water absorption of the test paper was measured at a contact time of 60 seconds and a test time of 22 ° C.
カチオン性高分子凝結剤と非フッ素系耐水剤の両方を用いた実施例１〜１４は、カチオン性高分子凝結剤もしくは非フッ素系耐水剤の添加を行わなかった比較例１〜４に比べ、耐水性に優れていた。 Examples 1 to 14 in which both the cationic polymer coagulant and the non-fluorine water resistant agent were used were compared with Comparative Examples 1 to 4 in which the cationic polymer coagulant or the non-fluorine water resistant agent was not added. It had excellent water resistance.
Claims (11)
非フッ素系耐水剤からなる第２剤と、
を備え、
用時に紙料と前記第１剤及び前記第２剤を順次混合して、紙料が抄紙された紙基材に耐水性を付与するための、抄紙用耐水剤キット。 The first agent consisting of a cationic polymer coagulant and
A second agent consisting of a non-fluorine-based water resistant agent,
With
A water resistant agent kit for papermaking, which sequentially mixes the paper material with the first agent and the second agent at the time of use to impart water resistance to the paper substrate on which the paper material is made.
前記工程１で得られた混合物と、非フッ素系耐水剤からなる第２剤とを混合する工程２と、
前記工程２で得られた混合物を抄紙する工程３と、
を備える、耐水紙の製造方法。 Step 1 of mixing the first agent consisting of a cationic polymer coagulant with a paper material,
Step 2 of mixing the mixture obtained in the above step 1 with a second agent made of a non-fluorine-based water resistant agent.
Step 3 of papermaking the mixture obtained in step 2 and
A method for manufacturing waterproof paper.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020057425A JP2021155886A (en) | 2020-03-27 | 2020-03-27 | Water resistant agent kit for paper making, water resistant paper, and method of producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020057425A JP2021155886A (en) | 2020-03-27 | 2020-03-27 | Water resistant agent kit for paper making, water resistant paper, and method of producing the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2021155886A true JP2021155886A (en) | 2021-10-07 |
Family
ID=77916979
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2020057425A Pending JP2021155886A (en) | 2020-03-27 | 2020-03-27 | Water resistant agent kit for paper making, water resistant paper, and method of producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2021155886A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116289311A (en) * | 2023-03-29 | 2023-06-23 | 浙江百斯特化工有限公司 | Preparation method of high-stability AKD sizing agent |
-
2020
- 2020-03-27 JP JP2020057425A patent/JP2021155886A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116289311A (en) * | 2023-03-29 | 2023-06-23 | 浙江百斯特化工有限公司 | Preparation method of high-stability AKD sizing agent |
| CN116289311B (en) * | 2023-03-29 | 2023-09-29 | 浙江百斯特化工有限公司 | Preparation method of high-stability AKD sizing agent |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2307613B1 (en) | Enhanced surface sizing of paper | |
| US8647470B2 (en) | Method for producing paper, paperboard and cardboard having high dry strength | |
| CN102076911B (en) | Composition and recording sheet with improved optical properties | |
| US10227731B2 (en) | Emulsification of alkenyl succinic anhydride with an amine-containing homopolymer of copolymer | |
| US8597466B2 (en) | Process for the production of paper, board and cardboard having high dry strength | |
| US7883603B2 (en) | Method for making paper and cardboard with high dry strength and resulting papers and cardboards | |
| US5145559A (en) | Production of paper, board and cardboard | |
| JPS62125098A (en) | Production of paper or cardboard | |
| JP2000504790A (en) | Manufacture of filled paper and compositions for use therein | |
| KR20160103067A (en) | Method for improving sizing efficiency of asa emulsion emulsified by a polymer emulsifier | |
| US5032226A (en) | Base paper for photographic layer support | |
| JP2021155886A (en) | Water resistant agent kit for paper making, water resistant paper, and method of producing the same | |
| KR100994091B1 (en) | Paper improver | |
| US20030127210A1 (en) | Sizing paper by wet-end addition of water dispersibility polyester | |
| JP6994343B2 (en) | Oil-resistant paper and oil-resistant paper manufacturing method | |
| JP2019039080A (en) | Oil-resistant paper and production method of the same | |
| JP5144330B2 (en) | Coating base paper for printing and method for producing coated paper | |
| WO2016182028A1 (en) | Greaseproof paper and method for producing same | |
| JPS58149398A (en) | Production of paper | |
| JPH08120592A (en) | Uncoated printing paper | |
| EP0119493A1 (en) | Use of copolymers of 2-acrylamido-2-methylpropane sulfonic acid for improving retention and dewatering in the manufacture of paper | |
| JP2003286681A (en) | Neutral paper sheet for printing | |
| Koskela et al. | Effect of water dispersible chemical derivatives on paper processing and performance | |
| Jing | Application of octadecylamine as an internal sizing agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20230214 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20231117 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20240109 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20240307 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20240507 |