JPH0368157B2 - - Google Patents
Info
- Publication number
- JPH0368157B2 JPH0368157B2 JP13294483A JP13294483A JPH0368157B2 JP H0368157 B2 JPH0368157 B2 JP H0368157B2 JP 13294483 A JP13294483 A JP 13294483A JP 13294483 A JP13294483 A JP 13294483A JP H0368157 B2 JPH0368157 B2 JP H0368157B2
- Authority
- JP
- Japan
- Prior art keywords
- component
- water
- starch
- paper
- mannitz
- 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.)
- Expired
Links
- 229920002472 Starch Polymers 0.000 claims description 66
- 235000019698 starch Nutrition 0.000 claims description 65
- 239000000203 mixture Substances 0.000 claims description 56
- 239000000178 monomer Substances 0.000 claims description 54
- 239000000654 additive Substances 0.000 claims description 51
- 239000008107 starch Substances 0.000 claims description 51
- 239000000047 product Substances 0.000 claims description 49
- 230000000996 additive effect Effects 0.000 claims description 32
- 150000001768 cations Chemical class 0.000 claims description 32
- 239000011347 resin Substances 0.000 claims description 32
- 229920005989 resin Polymers 0.000 claims description 32
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 31
- 239000007795 chemical reaction product Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 18
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 12
- 150000003335 secondary amines Chemical class 0.000 claims description 11
- 239000004480 active ingredient Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical group NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 55
- 238000006243 chemical reaction Methods 0.000 description 25
- 229940117913 acrylamide Drugs 0.000 description 21
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 20
- 230000000694 effects Effects 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 12
- 230000006872 improvement Effects 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 11
- 229920000881 Modified starch Polymers 0.000 description 10
- 125000002091 cationic group Chemical group 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 235000019426 modified starch Nutrition 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 150000001450 anions Chemical class 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 239000004368 Modified starch Substances 0.000 description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 6
- 239000012736 aqueous medium Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229940100198 alkylating agent Drugs 0.000 description 5
- 239000002168 alkylating agent Substances 0.000 description 5
- 125000003368 amide group Chemical group 0.000 description 5
- 239000003623 enhancer Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 150000004676 glycans Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 229920001282 polysaccharide Polymers 0.000 description 4
- 239000005017 polysaccharide Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000009172 bursting Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- -1 for example Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920001592 potato starch Polymers 0.000 description 3
- 238000005956 quaternization reaction Methods 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920001059 synthetic polymer Polymers 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229920006317 cationic polymer Polymers 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000005395 methacrylic acid group Chemical group 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- UDWYGWMSVGVBCG-UHFFFAOYSA-N 2-(dimethylamino)prop-2-enoic acid Chemical compound CN(C)C(=C)C(O)=O UDWYGWMSVGVBCG-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- UFQHFMGRRVQFNA-UHFFFAOYSA-N 3-(dimethylamino)propyl prop-2-enoate Chemical compound CN(C)CCCOC(=O)C=C UFQHFMGRRVQFNA-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920002261 Corn starch Polymers 0.000 description 1
- 229920001353 Dextrin Polymers 0.000 description 1
- 239000004375 Dextrin Substances 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 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
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 244000017020 Ipomoea batatas Species 0.000 description 1
- 235000002678 Ipomoea batatas Nutrition 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229920001938 Vegetable gum Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008120 corn starch Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 235000019425 dextrin Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- DENRZWYUOJLTMF-UHFFFAOYSA-N diethyl sulfate Chemical compound CCOS(=O)(=O)OCC DENRZWYUOJLTMF-UHFFFAOYSA-N 0.000 description 1
- 229940008406 diethyl sulfate Drugs 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 239000010800 human waste Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- WFKDPJRCBCBQNT-UHFFFAOYSA-N n,2-dimethylprop-2-enamide Chemical compound CNC(=O)C(C)=C WFKDPJRCBCBQNT-UHFFFAOYSA-N 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229940100445 wheat starch Drugs 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Paper (AREA)
Description
本発明は、製紙方法及び該方法の実施に用いる
のに適した製紙用添加剤に関する。
とくに、本発明は、従来公知のデンプン類及び
アクリル系樹脂もしくはその形成性単量体から導
かれた製紙用添加剤に比して、破裂強度、引張強
度、内部強度、表面強度などの紙質に関して顕著
に優れた紙質改善効果を賦与できるだけではな
く、たとえば内添サイズ剤、填料、顔料−染料
類、微細繊維などの如き製紙における各種添加剤
やパルプ中の微細繊維等に対する優れた歩留効果
も発揮でき、更には、優れた水効果の向上も達
成できて、抄紙機の操業性の改善やプレス・ロー
ルに於ける紙匹の剥離性の改善効果も示し、その
上、安価且つ製造容易である点でも工業的に有利
な製紙用添加剤及び製紙方法に関する。
更に詳しくは、本発明は下記(A)もしくは(A)′、
(A) デンプン類からなる成分（）とアクリル−
及び／又はメタアクリル−アミド系水溶性樹脂
成分（）との、重量比が（）：（）＝80：
20〜20：80である混合組成物、
もしくは
(A)′ デンプン類からなる成分（）と上記樹脂
成分（）形成性単量体成分（）′との、重
量比が（）：（）′＝80：20〜20：80である
組成物を、中性乃至酸性条件下、水溶性ラジカ
ル触媒の存在下で水溶性樹脂形成条件下に重合
して得られた組成物
の、ホルムアルデヒド及び第２級アミン類による
マンニツヒ反応生成物であつて、そのカチオン当
量が0.3ミリ当量／ｇ以上であるマンニツヒ化生
成物、又はカチオン当量が0.2ミリ当量／ｇ以上
である該マンニツヒ化生成物の四級化物を有効成
分として含有することを特徴とする製紙用添加剤
に関する。本発明は又、上記マンニツヒ化生成物
もしくはその四級化物を、抄紙機に送入する以前
の任意の過程に於て、紙料原料乃至調製紙料原料
中に、該原料中のパルプ乾燥重量に基いて約0.01
〜約５重量％配合し、PH約4.5〜約10の条件下で
抄造することを特徴とする製紙方法にも関する。
従来、紙質改善の目的で紙料原料乃至調製紙料
原料に、たとえば、デンプン類、植物性ガム類、
合成高分子類などを添加して抄紙することは広く
行われている。
未変性デンプン類は一般に極めて安価である点
で工業的に有利であるが、その反面、製紙用添加
剤とくには紙力増強剤としての単独利用において
は、合成高分子類特にアクリル−アミド系紙力増
強剤に比べて、その性能が可成り劣るという難点
がある。また、自己定着能を示すアニオン変性も
しくはカチオン変性デンプン類は変性前のデンプ
ン類に比して性能が向上するものの、その変性前
のデンプン類の低価格の利点を生かすためには、
その変性率には自ら制約をうけて比較的低い変性
率で利用する結果となり、製紙用添加剤として内
添利用した場合にはその歩留が不充分である難点
があり、ひいては製紙工程の自水中に未定着部分
の蓄積する傾向が増大し、その結果、腐敗その他
の不都合なトラブル発生の原因となる欠陥も回避
し難い。更に、未変性デンプン類や変性デンプン
類を製紙用添加剤として紙料に内添するに際して
は、その添加使用前に、溶解操作が必要となり、
これに要するエネルギー・コストならびに設備が
要求される不利益を伴い、且つ又、その負担は製
紙における無視し得ない負担増となる難点があ
る。
一方、合成高分子類特にアクリル−アミド系樹
脂類からなる製紙用添加剤に関しては多くの提案
がなされてきたが、その性能は良好である反面、
デンプン類からなる製紙用添加剤に比して高価に
つく点で工業的な不利益があり、これらデンプン
類からなる製紙用添加剤及びアクリルアミド系樹
脂類からなる製紙用添加剤の双方の長所を兼備し
た安価且つ高性能の製紙用添加剤の開発が望まれ
てきた。
このような技術的背景のもとに、両者の混合も
しくは反応による製紙用添加剤を開発しようとす
る提案もなされてきたが、満足すべき製紙用添加
剤を提供することは困難なのが実情である。
このような従来提案の一例として、特公昭38−
17051号には、水分散性多糖類と不飽和アミド及
び不飽和カルボン酸共重合体と前記多糖類と共重
合体間の付加物の３種の物質を主体とし、不飽和
アミドと不飽和カルボン酸の和は多糖類100部に
対し10〜300部であり、アミド基とカルボキシル
基のモル比が98〜30：２〜70であることを特徴と
する製紙用ビーター添加剤が提案されている。
又、他の一例として、特開昭58−41998号には、
少なくとも三種の一般式で特定された重合性ビニ
ル単量体の特定範囲のモル組成を有する重合性ビ
ニル単量体混合物を、該重合性ビニル単量体の混
合物の５〜90重量％の水溶性多糖類を溶存する水
溶液中で重合してなる紙力増強剤が提案されてい
る。
これら従来提案においては、水性媒体中デンプ
ン類溶液系でアクリル−アミド系単量体を重合も
しくは共重合させる点で共通している。そして、
これら従来提案には、このような重合生成物のビ
ーター添加剤や紙力増強剤用途が開示されている
だけであつて、該重合生成物のマンニツヒ反応生
成物や該マンニツヒ反応生成物の四級化物、更に
はその製紙用添加剤としての作用効果についてな
ぞ、勿論、全く開示されていないし且つ如何なる
示唆もなされていない。
本発明者等の検討によれば、これら従来提案の
タイプの重合生成物は、デンプン類を用いた分だ
け安価になる利点は得られるにしても、そのよう
な利点の実質的に得られるような量でデンプン類
を利用すると、その製紙用添加剤としての性能は
アクリルアミド系水溶性樹脂単独に比して著るし
く劣つた結果しか得られず、デンプン類及びアク
リル−アミド系水溶性樹脂各々の単独性能をそれ
らの原料組成比に配分した性能しか期待できない
ものであることがわかつた。斯くて、これら従来
提案のタイプの製紙用添加剤は、前述した双方の
長所を兼備した安価且つ高性能の製紙用添加剤の
要望には、到底、こたえ得ないことがわかつた。
更に、他の従来提案として、特開昭53−121886
号には、殿粉をアルカリ触媒の存在下、アクリル
アマイドと反応させて得られるカルバミルエチル
殿粉に、ホルムアルデヒド、二級アミンを別々
に、あるいはこれらの混合物を加え、マンニツヒ
反応を行わせることを特徴とするカチオン変性殿
粉の製造方法が提案されている。
この従来提案においては、たとえば、苛性ソー
ダ、苛性カリ、炭酸カリウム、トリメチルアミン
の如きアルカリ触媒の存在下に、殿粉をアクリル
アマイドと予め反応させることによりカルバミル
エチル殿粉を製造し、次いで、この予め形成され
たカルバミルエチル殿粉をマンニツヒ反応に賦す
ることを必須とするカチオン変性殿粉の製法が開
示されている。更に、該カチオン変性殿粉がカチ
オン性高分子凝集剤として有用であつて、上記カ
チオン変性前の原料カルバミルエチル殿粉に比し
て、屎尿処理場の余剰汚泥を対象にしたシリンダ
ーテスト法による沈降試験において、優れた凝集
効果を示したことが開示されている。
この従来提案においては、予め形成さたカルバ
ミルエチル殿粉のマンニツヒ化生成物であるカチ
オン変性殿粉が開示されているだけであつて、本
発明に特定されるような前記(A)もしくは(A)′組成
物は、直接にマンニツヒ反応に賦して得られる上
記(A)もしくは(A)′組成物のマンニツヒ反応生成物
についても、その四級化物についても、更にはこ
れら生成物の製紙用添加剤としての作用効果に関
しても、全く言及されていないし、示唆もされて
いない。更に、この提案による予め形成されたカ
ルバミルエチル殿粉をマンニツヒ化反応に賦して
得られるカチオン変性殿粉による破壊強度、引張
強度、内部強度、表面強度などの紙質に対する改
善効果はなお不満足であつて、一層の改善が望ま
れる。
本発明者等は、デンプン類及びアクリル系樹脂
もしくはその形成性単量体から導かれた従来公知
の製紙用添加剤における上述の如き不利益乃至欠
陥を克服できる製紙用添加剤及び製紙方法を開発
すべく研究を行つてきた。
その結果、前記(A)もしくは(A)′組成物を、直接
にマンニツヒ反応に賦して得られるマンニツヒ生
成物であつて、そのカチオン当量が0.3ミリ当
量／ｇ以上であるマンニツヒ化生成物、又はカチ
オン当量が0.2ミリ当量／ｇ以上である該マンニ
ツヒ化生成物の四級化物が、実質的な量でデンプ
ン類からなる成分（）を含有するにも拘わら
ず、デンプン類成分を含有しないアクリル−及
び／又はメタアクリル−アミド系樹脂製紙用添加
剤にまさるとも劣らない優れた製紙用添加剤性能
を示すことを発見した。
更に、デンプン類及びアクリル−及び／又はメ
タアクリル−アミド系樹脂もしくはその形成性単
量体から導かれた従来製紙用添加剤に比して、上
記マンニツヒ化生成物もしくはその四級化物を有
効成分とする本発明製紙用添加剤は、たとえば、
破裂強度、引張強度、内部強度、表面強度などの
紙質に関して顕著に優れた紙質改善効果で賦与で
きるだけではなく、たとえば内添サイズ剤、填
料、顔料・染料類、微細繊維などの如き製紙用の
各種添加剤やパルプ中の微細繊維等に対する優れ
た歩留効果も発揮できること、更に又、優れた
水効果の向上も達成できて、抄紙機の操業性の改
善やプレス・ロールに於ける紙匹の剥離性の改善
効果も示し、その上、安価且つ製造容易である点
においても工業的に有利な製紙用添加剤であるこ
とを発見した。
又更に、上記マンニツヒ化生成物もしくはその
四級化物を有効成分とする本発明製紙用添加剤
は、抄紙機に送入する以前の任意の製紙工程に於
て添加利用でき、抄紙機に送入する以前の任意の
過程で紙料原料乃至調製紙料原料中に添加でき
て、添加工程にとくべつな制約をうけない利点が
あり、該紙料原料乃至調製紙料原料中に該原料中
のパルプ乾燥重量に基いて約0.01〜約５重量％程
度の少量で配合し、PH約4.5〜約10の中性域抄紙
領域を含むPH条件下で造するだけで、上述の優れ
た諸作用効果を達成できることがわかつた。
前記(A)もしくは(A)′組成物を、直接にマンニツ
ヒ反応に賦して得ることができる、該(A)もしくは
(A)′組成物のホルムアルデヒド及び第２級アミン
類によるマンニツヒ反応生成物であつて、そのカ
チオン当量が0.3ミリ当量／ｇ以上であるマンニ
ツヒ化生成物、又はカチオン当量が0.2ミリ当
量／ｇ以上である該マンニツヒ化生成物の四級化
物からなる本発明製紙用添加剤の有効成分が、デ
ンプン類及びアクリル系樹脂もしくはその形成性
単量体から導かれた従来添加剤に比して顕著に優
れた諸作用効果を発揮できる作用機構の詳細は不
明であるが、後に多くの比較例と共に実施例を挙
げて実験的に示すとおり、その優れた改善効果か
らみて、従来添加剤とは異なつた反応生成物系が
形成されるものと推測される。
本発明者等の推測によれば、前記(A)組成物を直
接にマンニツヒ反応に賦して形成された反応生成
物系においては、例えば、デンプン類成分の水酸
基とアクリル−及び／又はメタアクリル−アミド
系水溶性樹脂成分のアミド基の間にホルムアルデ
ヒドが介在することによつて両成分を何等かの形
で化学的に結合して一成分系反応生成物に近い状
態の反応組成物系を形成する傾向があり、又、前
記(A)′組成物を直接にマンニツヒ反応に賦して形
成された反応生成物系においては、例えば、デン
プン類成分の水酸基、アクリル及び／又はメタア
クリル−アミド系水溶性樹脂成分形成性単量体が
グラフトしたデンプン類成分中の水酸基ならびに
アミド基、及び該単量体から導かれたアクリル−
及び／又はメタアクリル−アミド系水溶性樹脂成
分のアミド基の三者の間に、マンニツヒ化とホル
マリンによるアセタール結合形成が同時的に進行
して一成分系反応生成物に近い状態の反応組成物
系を形成する傾向があるものと考えられる。これ
に対して、従来提案の生成物系はデンプン類及び
アクリル−アミド系水溶性樹脂の単独性能を、そ
れらの反応原料組成比に配分した性能した示さな
いことからみて、デンプン類成分もしくは一部そ
の変性物とアクリル−及び／又はメタアクリル−
系水溶性樹脂もしくは一部その変成との混合物系
から主としてなる組成物系を形成する傾向がある
ものと推測され、それゆえに、後に比較例に示す
ように、本発明添加剤が示すような優れた作用効
果の発揮が達成し難いものと考えられる。
勿論、本発明は、上述の推測によつて何等の制
約も受けるものでないことを理解すべきである。
従つて、本発明の目的は改善された製紙用添加
剤を提供するにある。
本発明の他の目的は該添加剤を利用した改善さ
れた製紙方法を提供するにある。
本発明の上記目的及び更に多くの他の目的なら
びに利点は、以下の記載から一層明らかとなるで
あろう。
本発明の製紙用添加剤は、下記(A)もしくは(A)′、
(A) デンプン類からなる成分（）とアクリル−
及び／又はメタアクリル−アミド系水溶性樹脂
成分（）との、重量比が（）：（）＝80：
20〜20：80である混合組成物、
もしくは
(A)′ デンプン類からなる成分（）と上記樹脂
成分（）形成性単量体成分（）′との、重
量比が（）：（）′＝80：20〜20：80である
組成物を、中性乃至酸性条件下、水溶性ラジカ
ル触媒の存在下で水溶性樹脂形成条件下に重合
して得られた組成物
の、ホルムアルデヒド及び第２級アミン類による
マンニツヒ反応生成物であつて、そのカチオン当
量が0.3ミリ当量／ｇ以上であるマンニツヒ化生
成物、又はカチオン当量が0.2ミリ当量／ｇ以上
である該マンニツヒ化生成物の四級化物を有効成
分として含有する。
上記(A)組成物及び(A)′組成物におけるデンプン
類からなる成分（）の例としては、たとえばサ
ツマイモデンプン、バレイシヨデンプン、コムギ
デンプン、トウモロコシデンプン、タピオカデン
プンなどの如き生デンプン類；たとえばデキスト
リン、アルキルエーテル化デンプン、酸化デンプ
ン、アミノエチル化デンプン、シアノエチルエー
テル化デンプンなどの如き加工デンプン類；など
を例示することができる。これらは複数種併用す
ることもできる。これらデンプン類からなる成分
（）のうち、アニオンもしくはカチオン変成さ
れたデンプン類の利用がより好ましい。
又、上記(A)組成物におけるアクリル−及び／又
はメタアクリル−アミド系水溶性樹脂成分（）
もしくは上記(A)′組成物における該樹脂成分（）
形成性単量体成分（）′の例としては、下記(a)、
(b)及び(c)、
(a) アクリルアミド及びメタアクリルアミドより
成る群からえらばれた少なくとも一種の酸アミ
ド基含有単量体、
(b) 上記(a)と共重合可能なエチレン系不飽和カル
ボン酸もしくはその塩類、
(c) 上記(a)及び／又は(b)と共重合可能な上記(a)及
び(b)以外のビニル系単量体
からみちびかれた水溶性樹脂成分（）もしくは
その形成性単量体成分（）′を例示でき、上記
に於て、(a)は必須成分であり、(b)及び(c)は、所望
により、併用できる任意成分である。好ましい各
単量体の使用割合としては、総モル数に対する各
単量体のモル・パーセントの比で表わして、
(a)：(b)：(c)＝100〜50：０〜50：０〜30
の比を例示することができる。
上記例示のように、(a)単量体成分は、総モル数
の50モル・パーセント以上の主成分量を占めるの
が好ましい。より好ましくは総モル数の80モル・
パーセント以上である。(a)単量体成分が総モル数
の50モル・パーセント未満で過少量にすぎると紙
質改善の効果が低下する傾向があるので、上記例
示の如き主成分量で用いるのがよい。又、任意成
分である(b)単量体成分は、総モル数の50モル・パ
ーセント以下、より好ましくは約20モル・パーセ
ント以下の如き副成分で用いるのがよい。更に、
任意成分である(c)単量体成分は総モル数の30モ
ル・パーセント以下、より好ましくは約20モル・
パーセント以下の如き比較的少量で利用するのが
よい。
上記(a)単量体成分としては、アクリルアミドも
しくは主成分量のアクリルアミドからなる酸アミ
ド基含有単量体の利用がより好ましい。該(b)単量
体成分の例としては、アクリル酸、メタアクリル
酸、イタコン酸、マレイン酸、クロトン酸、フマ
ール酸及びこれらのアルカリ金属塩たとえばNa
塩やＫ塩もしくはアンモニウム塩類、などを例示
することができる。これらは複数種併用すること
もできる。これら例示の中では、アクリル酸、メ
タアクリル酸及びそれらの塩類の利用がより好ま
しい。又、上記(c)単量体成分の例としては、上記
(a)及び／又は(b)単量体成分と共重合可能な上記(a)
及び(b)以外の水酸基含有単量体、置換アミド基含
有単量体、アミノ基含有単量体、エチレン系ニト
リル化合物単量体などを例示することができる。
これらも複数種併用することができる。このよう
な(c)単量体成分の具体例としては、たとえばヒド
ロキシエチル−アクリレートもしくは−メタアク
リレート、Ｎ−メチル−アクリルアミドもしくは
−メタアクリルアミド、N.N−ジメチル−アク
リルアミドもしくは−メタアクリルアミド、ジメ
チルアミノ−アクリレートもしくは−メタアクリ
レート、ジメチルアミノプロピル−アクリレート
もしくは−メタアクリレート、アクリロニトリ
ル、メタアクリロニトリル、酢酸ビニル、スチレ
ンなどを例示することができる。
本発明に於て、(A)組成物の成分（）：成分
（）の重量比或は(A)′組成分の成分（）：成分
（）′の重量比は、80：20〜20：80、好ましくは
60：40〜20：80である。この重量比範囲を逸脱し
て成分（）が過剰量にすぎると紙質改善効果が
悪化し、また過少量にすぎると紙質改善効果の点
ではトラブルはないが、プレス・ロールにおける
紙匹の剥離性が不満足となり且つ低コストの利点
も失われるので、本発明に於ては、上記重量比範
囲で利用される。
本発明に於て、(A)組成物は前記例示の如きデン
プン類からなる成分（）と前記例示の如きアク
リル−及び／又はメタアクリル−アミド系水溶性
樹脂成分（）とを、上述の重量比範囲の混合物
となるように混合して形成することができる。
又、(A)′組成物は該成分（）と上記樹脂成分
（）形成性単量体成分（）′との、上述の重量
比範囲を充足する紙成物を、中性乃至酸性条件
下、水溶性ラジカル触媒、たとえば過硫酸カリウ
ム、過硫酸アンモニウムなどの如き水溶性ラジカ
ル触媒の存在下で水溶性樹脂形成条件下に重合し
て形成することができる。
このようなアルキル−及び／又はメタアクリル
−アミド系水溶性樹脂形成の手法それ自体はよく
知られており、本発明で利用できる。例えば、水
性媒体中、上記例示の如き水溶性ラジカル触媒の
存在下に、例えば約50℃〜約90℃の如き温度で重
合することができる。この際、(A)′組成物の場合
には、デンプン類からなる成分（）を水性媒体
中に分散させるか或は加温して糊化させた水性媒
体系で反応を行えばよい。又、重合度をコントロ
ールするために、例えばイソプロピルアルコール
の如き重合度調節剤を利用することができる。
本発明製紙用添加剤の有効成分であるマンニツ
ヒ化生成物又はその四級化物は、(A)組成物もしく
は(A)′組成物（本発明に於ては、両組成物の併用
の場合を包含する表現である）を、直接にホルム
アルデヒド及び第２級アミン類によるマンニツヒ
反応に賦することにより、更には、形成されたマ
ンニツヒ反応生成物をさらに四級化反応に賦する
ことにより容易に製造することができる。
マンニツヒ反応手段それ自体はよく知られてお
り、本発明で使用することができる。例えば、(A)
組成物もしくは(A)′組成物を、水性媒体中（これ
ら組成物が水性媒体中組成物の形である場合に
は、そのまま利用できる）、ホルムアルデヒド及
び第２級アミン類と、たとえば約20℃〜約80℃の
如き温度条件下で、形成されるマンニツヒ反応生
成物のカチオン当量が0.3ミリ当量／ｇ以上とな
るのに充分な時間たとえば約30分〜約10時間接触
せしめることにより、所望のマンニツヒ反応生成
物を形成することができる。反応モル比は適当に
選択できるが、例えば、成分（）及び（）も
しくは成分（）及び（）の合計重量に基い
て、たとえば約１〜約15重量パーセントの如きホ
ルムアルデヒド及びたとえば約1.5〜約35重量パ
ーセントの如き第２級アミン類の使用量を例示で
きる。
ホルムアルデヒドは、その水溶液の形すなわち
ホルマリンの形で利用するのが最も普通である。
又、利用する第２級アミン類の例としては、たと
えばジメチルアミン、ジエチルアミンの如きジ低
級アルキルアミン類及びジエタノールアミンの如
きジ低級アルカノールアミン類を好ましく例示で
きる。これらの中でも、ジメチルアミンの利用が
マンニツヒ化率の点でより好ましい。
本発明においては、たとえば上述のようにして
得ることのできる(A)組成物もしくは(A)′組成物の
ホルムアルデヒド及び第２級アミン類によるマン
ニツヒ反応生成物であつて、そのカチオン当量が
0.3ミリ当量／ｇ以上のマンニツヒ化生成物を用
いる。カチオン当量が0.3ミリ当量／ｇ未満過小
にすぎるマンニツヒ反応生成物は紙質改善性能、
水性向上作用及び歩留り向上作用などの効果が
不充分である。該カチオン当量の上限にはとくべ
つな制約はなく、本発明の製紙用添加剤を適用す
る紙料原料乃至調製紙料原料の種類、白水のコロ
イド化学的性質、さらには使用目的などに応じて
0.3ミリ当量／ｇ以上のカチオン当量領域に於て
適宜に選択設定できる。
上述のようにして得ることができる(A)組成物も
しくは(A)′組成物のホルムアルデヒド及び第２級
アミン類によるマンニツヒ反応生成物は、３級カ
チオン性生成物であつて、製紙工程のPHが硫酸ア
ルミニウムの存在下PH約4.5〜約6.5の範囲での利
用にとくに有用である。更に、このようなマンニ
ツヒ化生成物を更に四級化処理して得られるカチ
オン当量が0.2ミリ当量／ｇ以上である該マンニ
ツヒ化生成物の四級化物は、硫酸アルミニウムの
存在下もしくは不存在下PH約６〜約10の範囲での
利用にとくに有用である。
このような四級化処理手段それ自体はよく知ら
れており、本発明で利用することができる。例え
ば、特開昭57−67601号に開示の如き手法で、上
述のようにして得ることのできるマンニツヒ化生
成物を適当なアルキル化剤で更に処理することに
より、容易に形成することができる。利用するア
ルキル化剤の例としては、塩化メチル、ジメチル
硫酸、ジエチル硫酸、エチレンオキサイド、プロ
ピレンオキサイド、エピクロルヒドリン、ベンジ
ルクロライドなどを例示することができる。複数
種のアルキル化剤を利用することも可能である。
これらアルキル化剤の中でも、反応率や分子の嵩
ばりなどの点から塩化メチルやジメチル硫酸の如
き低級アルキル基を有するアルキル化剤の利用が
より好ましい。
本発明によれば、上述の如き(A)組成物もしくは
(A)′組成物のホルムアルデヒド及び第２級アミン
類によるマンニツヒ反応生成物であつて、そのカ
チオン当量が0.3ミリ当量／ｇ以上であるマンニ
ツヒ化生成物、又はカチオン当量が0.2ミリ当
量／ｇ以上である該マンニツヒ化生成物の四級化
物を、抄紙機に送入する以前の任意を過程に於
て、紙料原料乃至調製紙料原料中に該原料中のパ
ルプ乾燥重量に基いて約0.01〜約５重量％配合
し、PH約4.5〜約10の条件下で抄造することを特
徴とする製紙方法が提供できる。
本発明の製紙用添加剤を適用する製紙原料は、
特に限定されるものではなく、例えば通常用いら
れている製紙用パルプ、再生パルプ及び故紙パル
プの如き紙料原料のいずれにでも適用可能であ
る。また、これらの製紙原料中に、各種の目的で
添加される添加物、例えばサイズ剤、填料、顔
料、染料及びその他目的によつて添加される添加
物を含んだ調製紙料原料であつても同様に適用可
能である。
本発明の製紙用添加剤は、抄紙機に送入する以
前の任意の過程で紙料原料乃至は調製紙料原料に
添加でき、例えばビーターの任意の個所、更に
は、ヘツドボツクス、貯蔵槽などでも添加するこ
とができる。
該添加剤が３級カチオンであるカチオン当量が
0.3ミリ当量／ｇ以上のマンニツヒ化生成物の場
合には、硫酸アルミニウムを加わえた酸性抄紙、
すなわちPH約4.5〜約6.5の範囲に適用するのが好
ましい。また、該添加剤が４級カチオンであるカ
チオン当量が0.2ミリ当量／ｇ以上である該マン
ニツヒ化生成物の四級化物の場合には、硫酸アル
ミニウムが若干存在するかもしくは無添加であ
る、いわゆる中性抄造で、PH約６〜約10の範囲に
好ましく適用できる。
本発明の製紙用添加剤の使用量は、紙の種類、
要求される性能に応じて広範囲にわたり変えるこ
とができ、紙料原料乃至調製紙料原料に該原料中
のパルプ乾燥重量に対し、約0.01〜約５重量パー
セント、好ましくは約0.05〜約２重量パーセント
の範囲で添加される。
本発明の製紙用添加剤を以上の方法にて適用す
ることにより、従来のアクリル−アミド系製紙用
添加剤では達成し得なかつた操業性の改善、特に
プレスロールに於ける紙匹の剥離性が改善され、
一般に、この工程で多発する紙切れのトラブルを
極めて頻度の少いものにすることができる。ま
た、デンプン配合による紙質改善性能の低下はな
く、薬品費を大幅に低減させることができる。更
には、水剤、歩留剤としての幅広い用途にも適
用できるものである。
以下、実施例により本発明の説明をする。
比較例 １
デンプン類としてカチオンデンプン30ｇを水
270ｇ中に分散し（デンプン濃度10％）、60〜80℃
に加温して十分に溶解した後、アクリルアミド63
ｇ、アクリル酸７ｇ、水600ｇを加わえ、過硫酸
アンモニウム1.0重量パーセント／対単量体重量
を使用し、この際イソプロピルアルコールを併用
して重合度をコントロールし、デンプン溶液中で
上記木単量体の重合反応を行なつた。反応終了後
NaOHでPH6.5に調整し、濃度10％、粘度
8500cps、アニオン当量1.03meq／ｇの組成体を
得た。
比較例 ２−ａ
カチオンデンプン30ｇを水270ｇ中に分散し、
60〜80℃に加温して十分に溶解し、濃度10％のデ
ンプン溶液300ｇを調製する。これとは別に、ア
クリルアミド63ｇ、アクリル酸７ｇを水600ｇ中
に溶解し、過硫酸アンモニウム1.0重量％／対全
単量体重量を使用し、この際イソプロピルアルコ
ールを併用して重合度をコントロールし、反応終
了後NaOHでPH6.5に調整し、濃度10％、粘度
7600cps、アニオン当量1.41meq／ｇのアクリル
アミド系水溶性樹脂700ｇを得た。この水溶性樹
脂700ｇと上記カチオンデンプン溶液300ｇを十分
混合し、濃度10％、PH6.5、粘度8300cps、アニオ
ン当量1.02meq／ｇの組成体1000ｇを得た。
比較例 ２−ｂ
前記比較例２−ａで得られた水溶性樹脂成分
700ｇに37％ホルマリン水溶液16ｇ（0.197モル、
全単量体成分に対し20モル％）と50％ジメチルア
ミン水溶液24.8ｇ（0.276モル、全単量体成分に
対し28モル％）を加わえ、40℃で４時間マンニツ
ヒ反応を行ない、濃度10％、PH10.8、粘度
7200cps、カチオン当量2.80meq／ｇ、アニオン
当量1.00meq／ｇのマンニツヒ化物を調製した。
このマンニツヒ化物700ｇと10％のカチオンデン
プン溶液300ｇを十分に混合し、濃度10％、粘度
6800cps、カチオン当量1.80meq／ｇ、アニオン
当量0.93meq／ｇの混合物を得た。
比較例 ３
市販の馬鈴薯デンプン16.2ｇを水162ｇに加わ
え、70℃で加熱溶解させ、これを40℃とに冷却し
た後、撹拌下NaOH0.5ｇ、アクリルアミド7.1ｇ
を加わえて55℃で18時間加温した。このカルバミ
ルエチルデンプンに、37％ホルムアルデヒド水溶
液8.1ｇ、50％ジメチルアミン水溶液10.8ｇの混
合物を加わえ、40℃で４時間反応させてマンニツ
ヒ反応生成物を形成し、殿粉グルコース単位当り
カチオン化率44％のカチオン変成デンプンを得
た。
比較例 ４
比較例１で、単量体成分として70ｇのアクリル
アミドのみを用いた以外は全く同じ方法により、
アクリルアミドをカチオンデンプン溶液中で重合
し、得られた組成体1000ｇに37％ホルマリン水溶
液1.22ｇ（0.015モル、全単量体成分に対し1.53モ
ル）、50％ジメチルアミン水溶液1.89ｇ（0.021モ
ル、全単量体に対し2.13モル％）を加わえ、40％
で４時間マンニツヒ反応を行ない、濃度10％、PH
10.4、粘度8500cps、カチオン当量0.16eq／ｇ
（0.3meq／ｇ未満）のマンニツヒ化生成物を得
た。
比較例 ５
カチオンデンプン85ｇを水765ｇ中に分散し、
（デンプン濃度10％）、60〜80℃に加温して十分に
溶解した後、アクリルアミド15ｇを加わえ、過硫
酸アンモニウム1.0重量％／対全単量体重量を使
用し、デンプン溶液中でアクリルアミドの重合反
応を行なつた。得られた濃度10％の組成体（デン
プン成分：単量体成分＝85：15）1000ｇに37％ホ
ルマリン水溶液16ｇ（0.197モル、全単量体成分
に対し93.2モル％）、50％ジメチルアミン水溶液
24.8ｇ（0.276モル、全単量体成分に対し130モル
％）を加わえ、40℃で４時間マンニツヒ反応を行
ない、濃度10％、PH10.8、粘度4300cps、カチオ
ン当量1.83meq／ｇのマンニツヒ化生成物を得
た。
実施例 １
比較例１で得た組成体1000ｇに、37％ホルマリ
ン水溶液16ｇ（0.197モル、全単量体成分に対し
20モル％）と、50％ジメチルアミン水溶液24.8ｇ
（0.276モル、全単量体成分に対し28モル％）を加
わえ、40をで４時間マンニツヒ反応を行ない、濃
度10％、PH10.8、粘度7800cps、カチオン当量
1.82meq／ｇ、アニオン当量0.91meq／ｇのマン
ニツヒ化生成物を得た。
実施例 ２
比較例２−ａで得られた組成体1000ｇに、実施
例(1)と全く同じ条件で、全く同じ量のホルマリン
とジメチルアミンを用いてマンニツヒ反応を行な
い、濃度10％、PH10.8、粘度7700cps、カチオン
等量1.83meq／ｇ、アニオン当量0.92me9／ｇの
マンニツヒ化生成物を得た。
実施例 ３
比較例３と全く同じ原料組成で、実施例(1)と全
く同じ方法でマンニツヒ化生成物を調製した。得
られたマンニツヒ化生成物は濃度10％、PH10.8、
粘度7000cps、カチオン当量3.03meq／ｇであつ
た。
実施例 ４
比較例１で、単量体成分として70ｇのアクリル
アミドを用いた以外は全く同じ方法により、アク
リルアミドをカチオンデンプン溶液中で重合し、
得られた濃度10％の組成体1000ｇに実施例１と全
く同量のホルマリンとジメチルアミンを用いてマ
ンニツヒ反応を行なつた。さらにジメチル硫酸
34.8ｇ（0.276モル対ジメチルアミン100モル％）
を用い、特開昭57−67601開示の方法により４級
化反応を行ない、濃度10％、PH5.0、粘度
6200cps、全カチオン当量（PH3.0で測定）
1.79meq／ｇ、４級カチオン当量（PH10.0で測定）
1.32meq／ｇのマンニツヒ４級化性物を得た。
実施例 ５
いわゆる酸性抄紙条件下に於ける比較を行なう
目的で以下に述べる試験を実施した。
水度450c.c.の晒広葉樹パルプに上記比較例(1)
〜(6)及び実施例(1)〜(3)の製品を、硫酸アルミニウ
ムを用いてPH4.5及びPH5.5に調整した紙料量に対
してパルプ絶乾重量当り0.5重量パーセント添加
し、常法通りタツピースタンダードシートマシン
にて坪量60ｇ／m2の紙を抄紙し、加圧脱水、乾燥
後JIS及びタツピー方式に従つて、得られた乾燥
紙葉の諸強度を測定した結果、表−１〜３に示す
値を得た。尚、評価項目並びに試験法は以下に示
す通りである。
試験項目並びに試験方法：−
破裂強度：JIS Ｐ−8112
引張強度：JIS Ｐ−8131
内部強度：Tappi RC−308インターナル・ボ
ド・テスター
表面強度：JIS ｐ−8129（IGT法）TV＝20、振
子法
The present invention relates to a papermaking process and papermaking additives suitable for use in carrying out the process. In particular, the present invention improves paper properties such as bursting strength, tensile strength, internal strength, and surface strength, compared to conventional papermaking additives derived from starches and acrylic resins or their forming monomers. It not only has a remarkable effect on improving paper quality, but also has an excellent retention effect on various additives in paper manufacturing such as internal sizing agents, fillers, pigments and dyes, fine fibers, and fine fibers in pulp. In addition, it is possible to improve the water efficiency, improve the operability of paper machines, and improve the peelability of the paper web in presses and rolls. Moreover, it is inexpensive and easy to manufacture. The present invention relates to a papermaking additive and a papermaking method that are industrially advantageous in certain respects. More specifically, the present invention comprises the following (A) or (A)', (A) a component () consisting of starch and an acrylic-
and/or methacryl-amide water-soluble resin component (), the weight ratio is (): () = 80:
A mixed composition having a weight ratio of 20 to 20:80, or (A)′ the weight ratio of the starch component () and the resin component ()-forming monomer component ()′; Formaldehyde and secondary A Mannitz reaction product with a class amine having a cation equivalent of 0.3 meq/g or more, or a quaternized product of the Mannitshu reaction product having a cation equivalent of 0.2 meq/g or more. The present invention relates to a papermaking additive characterized by containing as an active ingredient. The present invention also provides that the above-mentioned Manniching product or its quaternized product is added to a paper stock raw material or a prepared paper stock raw material in an arbitrary process before being fed into a paper machine, by the dry weight of pulp in the raw material. approximately 0.01 based on
It also relates to a paper manufacturing method characterized in that the paper is made under conditions of a pH of about 4.5 to about 10. Conventionally, starches, vegetable gums, etc. have been added to paper materials or prepared paper materials for the purpose of improving paper quality.
It is widely practiced to make paper by adding synthetic polymers and the like. Unmodified starches are industrially advantageous in that they are generally extremely cheap, but on the other hand, when used alone as papermaking additives, especially paper strength enhancers, synthetic polymers, especially acryl-amide paper The drawback is that its performance is considerably inferior to that of force enhancers. In addition, although anionically modified or cationically modified starches that exhibit self-fixing ability have improved performance compared to unmodified starches, in order to take advantage of the low cost of unmodified starches,
The modification rate is subject to its own limitations, and as a result, it is used at a relatively low modification rate, and when it is used internally as a papermaking additive, the yield is insufficient, and as a result, the papermaking process can be automated. It is also difficult to avoid defects that increase the tendency for unfixed parts to accumulate in the water, resulting in rotting and other undesirable problems. Furthermore, when adding unmodified starches or modified starches to paper stocks as papermaking additives, a dissolution operation is required before addition and use.
This is accompanied by disadvantages in terms of energy costs and equipment requirements, and also has the drawback of adding to the burden of paper manufacturing which cannot be ignored. On the other hand, many proposals have been made regarding papermaking additives made of synthetic polymers, especially acryl-amide resins, but while their performance is good,
There is an industrial disadvantage in that it is more expensive than papermaking additives made of starches. It has been desired to develop a papermaking additive that is both inexpensive and has high performance. Based on this technical background, proposals have been made to develop papermaking additives by mixing or reacting the two, but the reality is that it is difficult to provide a satisfactory papermaking additive. be. An example of such a conventional proposal is the
No. 17051 mainly contains three types of substances: a water-dispersible polysaccharide, an unsaturated amide, an unsaturated carboxylic acid copolymer, and an adduct between the polysaccharide and the copolymer. A beater additive for paper manufacturing has been proposed, characterized in that the sum of acids is 10 to 300 parts per 100 parts of polysaccharide, and the molar ratio of amide groups to carboxyl groups is 98 to 30:2 to 70. .
Also, as another example, in Japanese Patent Application Laid-open No. 58-41998,
A polymerizable vinyl monomer mixture having a molar composition in a specific range of polymerizable vinyl monomers specified by at least three general formulas is added to a polymerizable vinyl monomer mixture having a water solubility of 5 to 90% by weight of the polymerizable vinyl monomer mixture. Paper strength enhancers have been proposed that are polymerized in an aqueous solution containing dissolved polysaccharides. These conventional proposals have in common that an acrylamide monomer is polymerized or copolymerized in a starch solution system in an aqueous medium. and,
These conventional proposals only disclose the use of such polymerization products as beater additives and paper strength enhancers, and they only disclose the use of the polymerization product as a beater additive or paper strength enhancer. Of course, there is no disclosure or any suggestion whatsoever regarding the compound and its effects as a papermaking additive. According to the studies of the present inventors, although these conventionally proposed types of polymerization products have the advantage of being cheaper due to the use of starch, they do not seem to be able to substantially obtain such advantages. If starch is used in a large amount, its performance as a papermaking additive is significantly inferior to that of acrylamide water-soluble resin alone, and starch and acrylamide water-soluble resin each It was found that the performance that can be expected is only when the independent performance of the material is distributed to the composition ratio of the raw materials. Therefore, it has been found that these conventionally proposed types of papermaking additives cannot meet the demand for an inexpensive and high-performance papermaking additive that combines the above-mentioned advantages. Furthermore, as another conventional proposal, Japanese Patent Application Laid-Open No. 53-121886
No. 1, the Mannitz reaction is carried out by adding formaldehyde and a secondary amine separately or a mixture thereof to carbamylethyl starch obtained by reacting the starch with acrylamide in the presence of an alkali catalyst. A method for producing cationically modified starch has been proposed. In this prior proposal, carbamyl ethyl starch is produced by pre-reacting the starch with acrylamide in the presence of an alkaline catalyst such as, for example, caustic soda, caustic potash, potassium carbonate, trimethylamine, and then this pre-formed A method for producing a cationically modified starch is disclosed, which requires subjecting the resulting carbamylethyl starch to a Mannitz reaction. Furthermore, the cationically modified starch is useful as a cationic polymer flocculant, and compared to the raw material carbamylethyl starch before cationically modified, it has been found that the starch is more useful as a cationic polymer flocculant than the raw material carbamylethyl starch before being cationically modified, according to a cylinder test method targeting surplus sludge from a human waste treatment plant. It is disclosed that it showed an excellent flocculation effect in a sedimentation test. This prior proposal only discloses a cationically modified starch which is a mannification product of a preformed carbamylethyl starch, and only discloses the above-mentioned (A) or (2) as specified in the present invention. A)' compositions include the Mannitz reaction products of the above-mentioned (A) or (A)' compositions obtained by directly subjecting them to the Mannitz reaction, as well as their quaternized products, as well as paper-making products of these products. There is no mention or suggestion of the function or effect as an additive for use. Furthermore, the improvement effects on paper quality such as breaking strength, tensile strength, internal strength, and surface strength of the cationically modified starch obtained by subjecting the preformed carbamylethyl starch to the mannichization reaction according to this proposal are still unsatisfactory. Further improvements are desired. The present inventors have developed a papermaking additive and a papermaking method that can overcome the disadvantages and defects described above in conventional papermaking additives derived from starches and acrylic resins or their forming monomers. I've been doing research to find out. As a result, a Mannitz product obtained by directly subjecting the composition (A) or (A)' to a Mannitz reaction, the Mannitz reaction product having a cation equivalent of 0.3 milliequivalents/g or more, Or, even though the quaternized product of the manniciform product having a cation equivalent of 0.2 milliequivalents/g or more contains a substantial amount of a component () consisting of starch, it is an acrylic product that does not contain a starch component. - and/or methacryl-amide resins It has been discovered that the present invention exhibits excellent papermaking additive performance comparable to that of methacrylamide-based papermaking additives. Furthermore, compared to conventional papermaking additives derived from starches and acrylic- and/or methacryl-amide resins or their forming monomers, the above-mentioned mannification products or quaternized products thereof are used as active ingredients. The papermaking additive of the present invention is, for example,
Not only can it provide outstanding paper quality improvement effects such as bursting strength, tensile strength, internal strength, and surface strength, but it can also be used to improve paper quality, such as internal sizing agents, fillers, pigments/dyes, fine fibers, etc. It is possible to exhibit an excellent retention effect on additives and fine fibers in the pulp, and it is also possible to achieve an excellent improvement in the water effect, improving the operability of paper machines and improving the paper web in presses and rolls. It has been discovered that it is an industrially advantageous paper-making additive that exhibits the effect of improving peelability, and is also inexpensive and easy to manufacture. Furthermore, the paper-making additive of the present invention containing the above-mentioned Mannitz-formed product or its quaternized product as an active ingredient can be used as an additive in any paper-making process before being fed into a paper machine; It has the advantage that it can be added to paper stock raw materials or prepared paper stock raw materials in any process before adding, and there are no particular restrictions on the addition process, and the pulp in the raw materials can be added to By simply blending in a small amount of about 0.01 to about 5% by weight based on dry weight and manufacturing under pH conditions including the neutral papermaking region of about 4.5 to about 10, the above-mentioned excellent effects can be achieved. I found out that it can be achieved. The above (A) or (A)′ composition can be obtained by directly subjecting the above (A) or (A)′ composition to a Mannitz reaction.
(A)' A Mannitz reaction product with formaldehyde and secondary amines of the composition, which has a cation equivalent of 0.3 meq/g or more, or a mannitz reaction product with a cation equivalent of 0.2 meq/g or more The active ingredient of the paper-making additive of the present invention, which consists of the quaternized product of the mannification product, is significantly more active than that of conventional additives derived from starches and acrylic resins or their forming monomers. Although the details of the mechanism of action that enables it to exhibit its various excellent effects are unknown, as will be shown experimentally later with many comparative examples and examples, its excellent improvement effects indicate that it is different from conventional additives. It is assumed that a reaction product system is formed. According to the present inventors' speculation, in the reaction product system formed by directly subjecting the composition (A) to the Mannitz reaction, for example, hydroxyl groups of starch components and acrylic and/or methacrylic - By intervening formaldehyde between the amide groups of the amide-based water-soluble resin component, both components are chemically bonded in some way to create a reaction composition system that is close to a one-component reaction product. In addition, in the reaction product system formed by directly subjecting the composition (A)' to the Mannitz reaction, for example, hydroxyl groups, acrylic and/or methacrylamide of starch components The hydroxyl group and amide group in the starch component grafted with the water-soluble resin component-forming monomer, and the acrylic group derived from the monomer.
and/or a reaction composition in which Mannichization and acetal bond formation by formalin proceed simultaneously between the three amide groups of the methacrylamide-based water-soluble resin component, resulting in a state close to a one-component reaction product. It is thought that there is a tendency to form a system. On the other hand, the product systems proposed so far do not show the individual performance of starches and acryl-amide water-soluble resins, but the performance that is distributed to their reaction raw material composition ratios. Modified products thereof and acrylic and/or methacrylic
It is presumed that there is a tendency to form a composition system mainly composed of a water-soluble resin or a mixture system with a part of its modification, and therefore, as shown in the comparative examples later, the additive of the present invention does not have the excellent properties. It is considered that it is difficult to achieve the desired effects. Of course, it should be understood that the present invention is not limited in any way by the above assumptions. Accordingly, it is an object of the present invention to provide an improved papermaking additive. Another object of the present invention is to provide an improved papermaking process using the additive. The above objects and many other objects and advantages of the present invention will become more apparent from the following description. The papermaking additive of the present invention comprises the following (A) or (A)′, (A) a component () consisting of starch and acrylic-
and/or methacryl-amide water-soluble resin component (), the weight ratio is (): () = 80:
A mixed composition having a weight ratio of 20 to 20:80, or (A)′ the weight ratio of the starch component () and the resin component ()-forming monomer component ()′; Formaldehyde and secondary A Mannitz reaction product with a class amine having a cation equivalent of 0.3 meq/g or more, or a quaternized product of the Mannitshu reaction product having a cation equivalent of 0.2 meq/g or more. Contains as an active ingredient. Examples of the component () consisting of starches in the compositions (A) and (A)' are raw starches such as sweet potato starch, potato starch, wheat starch, corn starch, tapioca starch; Examples include modified starches such as dextrin, alkyl etherified starch, oxidized starch, aminoethylated starch, cyanoethyl etherified starch, and the like. These can also be used in combination. Among these components () consisting of starches, it is more preferable to use anionically or cationically modified starches. In addition, the acrylic and/or methacrylamide water-soluble resin component () in the composition (A) above
Or the resin component () in the above (A)′ composition
Examples of the formative monomer component ()′ are the following (a),
(b) and (c), (a) at least one acid amide group-containing monomer selected from the group consisting of acrylamide and methacrylamide, (b) ethylenically unsaturated carbon which is copolymerizable with (a) above; (c) A water-soluble resin component () derived from a vinyl monomer other than (a) and (b) above that can be copolymerized with (a) and/or (b) above, or The forming monomer component ()' can be exemplified. In the above, (a) is an essential component, and (b) and (c) are optional components that can be used in combination as desired. The preferred ratio of each monomer to be used is expressed as a molar percent ratio of each monomer to the total number of moles, (a):(b):(c)=100-50:0-50:0. An example is a ratio of ~30. As exemplified above, the monomer component (a) preferably accounts for 50 mol percent or more of the total number of moles. More preferably 80 moles of the total number of moles.
% or more. If the amount of the monomer component (a) is too small (less than 50 mol percent of the total number of moles), the effect of improving paper quality tends to decrease, so it is preferable to use the amount of the main component as exemplified above. The optional monomer component (b) is preferably used in an amount of 50 mole percent or less, more preferably about 20 mole percent or less, of the total number of moles. Furthermore,
The optional monomer component (c) is less than 30 mole percent of the total number of moles, more preferably about 20 mole percent.
It is best to use relatively small amounts, such as less than 1%. As the monomer component (a), it is more preferable to use acrylamide or an acid amide group-containing monomer consisting of acrylamide in the main component amount. Examples of the monomer component (b) include acrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonic acid, fumaric acid, and alkali metal salts thereof, such as Na
Examples include salts, K salts, and ammonium salts. These can also be used in combination. Among these examples, it is more preferable to use acrylic acid, methacrylic acid, and salts thereof. In addition, examples of the monomer component (c) above include the above
(a) and/or (b) The above (a) that can be copolymerized with the monomer component
Examples include hydroxyl group-containing monomers, substituted amide group-containing monomers, amino group-containing monomers, and ethylene-based nitrile compound monomers other than (b).
Multiple types of these can also be used in combination. Specific examples of such monomer component (c) include, for example, hydroxyethyl-acrylate or -methacrylate, N-methyl-acrylamide or -methacrylamide, N-dimethyl-acrylamide or -methacrylamide, dimethylamino-acrylate. Examples include -methacrylate, dimethylaminopropyl acrylate or -methacrylate, acrylonitrile, methacrylonitrile, vinyl acetate, and styrene. In the present invention, the weight ratio of (A) component ():component () of the composition or the weight ratio of component ():component ()' of (A)'composition is 80:20 to 20: 80, preferably
The hours are 60:40 to 20:80. If the weight ratio exceeds this range and the amount of component () is too large, the paper quality improvement effect will worsen, and if it is too small, there will be no problem in terms of the paper quality improvement effect, but the paper web will be difficult to peel off in presses and rolls. Since the weight ratio becomes unsatisfactory and the advantage of low cost is also lost, the above weight ratio range is used in the present invention. In the present invention, the composition (A) consists of a component () consisting of starch as exemplified above and an acrylic- and/or methacrylamide-based water-soluble resin component () as exemplified above. They can be formed by mixing to form a mixture with a range of ratios.
In addition, (A)' composition is a paper product that satisfies the above-mentioned weight ratio range of the component () and the resin component ()-forming monomer component ()' under neutral to acidic conditions. can be formed by polymerization under conditions for forming a water-soluble resin in the presence of a water-soluble radical catalyst such as potassium persulfate, ammonium persulfate, and the like. The method of forming such an alkyl- and/or methacrylamide-based water-soluble resin is itself well known and can be utilized in the present invention. For example, the polymerization can be carried out in an aqueous medium in the presence of a water-soluble radical catalyst such as those exemplified above at a temperature such as from about 50°C to about 90°C. At this time, in the case of the composition (A)', the reaction may be carried out in an aqueous medium system in which the component () consisting of starch is dispersed in an aqueous medium or gelatinized by heating. Further, in order to control the degree of polymerization, a degree of polymerization regulator such as isopropyl alcohol can be used. The Mannitz-formed product or its quaternized product, which is the active ingredient of the paper-making additive of the present invention, can be used in the composition (A) or the composition (A)' (in the present invention, when both compositions are used together). ) can be easily produced by subjecting directly to a Mannitz reaction with formaldehyde and secondary amines, and further subjecting the formed Mannitz reaction product to a quaternization reaction. can do. The Mannitz reaction procedure itself is well known and can be used in the present invention. For example, (A)
The composition or (A)' composition in an aqueous medium (if these compositions are in the form of a composition in an aqueous medium, they can be used as such) with formaldehyde and secondary amines, for example at about 20°C. to about 80° C. for a sufficient period of time, such as from about 30 minutes to about 10 hours, such that the cation equivalent of the Mannitz reaction product formed is 0.3 meq/g or more. Mannitz reaction products can be formed. The reaction molar ratios can be suitably selected, but include, for example, from about 1 to about 15 weight percent formaldehyde and from about 1.5 to about 35 weight percent formaldehyde, for example, based on the total weight of components () and () or components () and (). The amount of secondary amines to be used, such as weight percent, may be exemplified. Formaldehyde is most commonly utilized in the form of its aqueous solution, ie formalin.
Preferable examples of the secondary amines to be used include di-lower alkylamines such as dimethylamine and diethylamine, and di-lower alkanolamines such as diethanolamine. Among these, use of dimethylamine is more preferable in terms of the rate of Mannich conversion. In the present invention, the Mannitz reaction product of formaldehyde and secondary amines of the composition (A) or the composition (A)', which can be obtained as described above, is used, for example, and the cation equivalent thereof is
More than 0.3 meq/g of mannichized product is used. The Mannitz reaction product with a cation equivalent of less than 0.3 meq/g has poor paper quality improvement performance.
Effects such as water property improvement effect and retention improvement effect are insufficient. There is no particular restriction on the upper limit of the cation equivalent, and it depends on the type of paper stock material or prepared paper stock material to which the papermaking additive of the present invention is applied, the colloidal chemical properties of white water, and the purpose of use.
It can be selected and set as appropriate in the cation equivalent range of 0.3 milliequivalent/g or more. The Mannitz reaction product of formaldehyde and secondary amines of composition (A) or composition (A)′ which can be obtained as described above is a tertiary cationic product and is a tertiary cationic product, is particularly useful in the presence of aluminum sulfate at a pH ranging from about 4.5 to about 6.5. Furthermore, the quaternized product of the manniated product, which has a cation equivalent of 0.2 milliequivalents/g or more obtained by further quaternizing the manniated product, can be treated in the presence or absence of aluminum sulfate. It is particularly useful for applications in the pH range of about 6 to about 10. Such quaternization treatment means themselves are well known and can be utilized in the present invention. For example, they can be readily formed by further treatment of the mannification product obtainable as described above with a suitable alkylating agent, in a manner such as that disclosed in JP-A-57-67601. Examples of the alkylating agent to be used include methyl chloride, dimethyl sulfate, diethyl sulfate, ethylene oxide, propylene oxide, epichlorohydrin, and benzyl chloride. It is also possible to utilize multiple types of alkylating agents.
Among these alkylating agents, it is more preferable to use alkylating agents having a lower alkyl group such as methyl chloride and dimethyl sulfate from the viewpoint of reaction rate and bulkiness of molecules. According to the present invention, the composition (A) as described above or
(A)' A Mannitz reaction product with formaldehyde and secondary amines of the composition, which has a cation equivalent of 0.3 meq/g or more, or a mannitz reaction product with a cation equivalent of 0.2 meq/g or more The quaternized product of the Mannitz-formed product is added to the paper stock material or the prepared paper stock material in any process prior to feeding into the paper machine, based on the dry weight of the pulp in the material. It is possible to provide a paper manufacturing method characterized in that the paper is made under conditions of a pH of about 4.5 to about 10. The papermaking raw materials to which the papermaking additive of the present invention is applied are:
The present invention is not particularly limited, and can be applied to any paper material such as commonly used papermaking pulp, recycled pulp, and waste paper pulp. In addition, even if these papermaking raw materials contain additives added for various purposes, such as sizing agents, fillers, pigments, dyes, and other additives added for purposes, Similarly applicable. The papermaking additive of the present invention can be added to paper stock raw materials or prepared paper stock raw materials in any process before being fed into the paper machine, for example, at any location in the beater, furthermore, in the head box, storage tank, etc. Can be added. The cation equivalent of the additive is a tertiary cation is
In the case of mannitzization products of 0.3 milliequivalents/g or more, acid papermaking with addition of aluminum sulfate,
That is, it is preferably applied to a pH range of about 4.5 to about 6.5. In addition, in the case of a quaternized product of the Mannitz-formed product in which the additive is a quaternary cation and the cation equivalent is 0.2 milliequivalent/g or more, aluminum sulfate is slightly present or is not added. It is a neutral paper making and can be preferably applied to a pH range of about 6 to about 10. The amount of the papermaking additive of the present invention is determined by the type of paper,
It can be varied over a wide range depending on the performance required, and may be added to the paper stock or prepared stock stock from about 0.01 to about 5 percent by weight, preferably from about 0.05 to about 2 percent by weight, based on the dry weight of the pulp in the material. It is added within the range of By applying the papermaking additive of the present invention in the above-described manner, it is possible to improve operability, which could not be achieved with conventional acrylamide papermaking additives, and in particular to improve the peelability of the paper web in press rolls. has been improved,
In general, the frequency of paper breakage problems that occur frequently in this process can be minimized. In addition, the paper quality improvement performance does not deteriorate due to the addition of starch, and chemical costs can be significantly reduced. Furthermore, it can be applied to a wide range of uses as water preparations and retention agents. The present invention will be explained below with reference to Examples. Comparative example 1 30g of cationic starch as starch was added to water.
Dispersed in 270g (starch concentration 10%), 60-80℃
After heating to sufficiently dissolve the acrylamide 63
g, 7 g of acrylic acid, and 600 g of water were added, and ammonium persulfate was used at a concentration of 1.0% by weight/monomer weight. At this time, isopropyl alcohol was also used to control the degree of polymerization, and the above wood monomers were added in the starch solution. A polymerization reaction was carried out. After the reaction
Adjusted to PH6.5 with NaOH, concentration 10%, viscosity
A composition of 8500 cps and anion equivalent of 1.03 meq/g was obtained. Comparative Example 2-a 30g of cationic starch was dispersed in 270g of water,
Heat to 60-80°C to fully dissolve and prepare 300g of starch solution with a concentration of 10%. Separately, 63 g of acrylamide and 7 g of acrylic acid were dissolved in 600 g of water, and ammonium persulfate was used at a concentration of 1.0% by weight/based on the total monomer weight. At this time, isopropyl alcohol was also used to control the degree of polymerization, and the reaction was carried out. After completion, adjust the pH to 6.5 with NaOH, concentration 10%, viscosity
700 g of acrylamide water-soluble resin having 7600 cps and an anion equivalent of 1.41 meq/g was obtained. 700 g of this water-soluble resin and 300 g of the above cationic starch solution were thoroughly mixed to obtain 1000 g of a composition having a concentration of 10%, a pH of 6.5, a viscosity of 8300 cps, and an anion equivalent of 1.02 meq/g. Comparative Example 2-b Water-soluble resin component obtained in Comparative Example 2-a
16g of 37% formalin aqueous solution (0.197mol,
(20 mol% based on the total monomer components) and 24.8 g (0.276 mol, 28 mol% based on the total monomer components) of a 50% dimethylamine aqueous solution were added, and the Mannitz reaction was carried out at 40°C for 4 hours to obtain a concentration of 10. %, PH10.8, viscosity
A mannissa compound with 7200 cps, cation equivalent of 2.80 meq/g, and anion equivalent of 1.00 meq/g was prepared.
Thoroughly mix 700 g of this mannissa and 300 g of a 10% cationic starch solution to obtain a solution with a concentration of 10% and a viscosity of 10%.
A mixture of 6800 cps, cation equivalent: 1.80 meq/g, and anion equivalent: 0.93 meq/g was obtained. Comparative Example 3 16.2 g of commercially available potato starch was added to 162 g of water and dissolved by heating at 70°C. After cooling to 40°C, 0.5 g of NaOH and 7.1 g of acrylamide were added under stirring.
was added and heated at 55°C for 18 hours. A mixture of 8.1 g of a 37% formaldehyde aqueous solution and 10.8 g of a 50% dimethylamine aqueous solution was added to the carbamyl ethyl starch and reacted at 40°C for 4 hours to form a Mannitz reaction product, resulting in cationization per starch glucose unit. Cationically modified starch with a percentage of 44% was obtained. Comparative Example 4 By the same method as in Comparative Example 1 except that only 70 g of acrylamide was used as the monomer component,
Acrylamide was polymerized in a cationic starch solution, and 1.22 g of a 37% formalin aqueous solution (0.015 mol, 1.53 mol based on the total monomer component) and 1.89 g of a 50% dimethylamine aqueous solution (0.021 mol, total) were added to 1000 g of the resulting composition. 40%
Perform the Mannitz reaction for 4 hours at a concentration of 10% and pH
10.4, viscosity 8500cps, cation equivalent 0.16eq/g
(less than 0.3meq/g) of the mannichized product was obtained. Comparative Example 5 85g of cationic starch was dispersed in 765g of water,
(starch concentration 10%), add 15 g of acrylamide after heating to 60-80°C, and use ammonium persulfate 1.0% by weight/total monomer weight to dissolve acrylamide in the starch solution. A polymerization reaction was carried out. To 1000 g of the obtained composition with a concentration of 10% (starch component: monomer component = 85:15), 16 g of a 37% formalin aqueous solution (0.197 mol, 93.2 mol% based on the total monomer components) and a 50% dimethylamine aqueous solution were added.
24.8 g (0.276 mol, 130 mol % based on the total monomer components) was added, and the Mannitz reaction was carried out at 40°C for 4 hours. A reaction product was obtained. Example 1 16 g of a 37% formalin aqueous solution (0.197 mol, based on the total monomer components) was added to 1000 g of the composition obtained in Comparative Example 1.
20 mol%) and 24.8 g of 50% dimethylamine aqueous solution
(0.276 mol, 28 mol% based on the total monomer components) was added and subjected to Mannitz reaction at 40°C for 4 hours, concentration 10%, pH 10.8, viscosity 7800 cps, cation equivalent.
A mannification product with an anion equivalent of 0.91 meq/g and an anion equivalent of 1.82 meq/g was obtained. Example 2 1000 g of the composition obtained in Comparative Example 2-a was subjected to Mannitz reaction under exactly the same conditions as in Example (1) using exactly the same amounts of formalin and dimethylamine, resulting in a concentration of 10% and a pH of 10. 8, a mannichilation product with a viscosity of 7700 cps, a cation equivalent of 1.83 meq/g, and an anion equivalent of 0.92 me9/g was obtained. Example 3 A manniciform product was prepared using exactly the same raw material composition as in Comparative Example 3 and in exactly the same manner as in Example (1). The resulting manniciform product had a concentration of 10%, a pH of 10.8,
The viscosity was 7000 cps and the cation equivalent was 3.03 meq/g. Example 4 Acrylamide was polymerized in a cationic starch solution using exactly the same method as in Comparative Example 1 except that 70 g of acrylamide was used as the monomer component,
A Mannitz reaction was carried out on 1000 g of the obtained composition having a concentration of 10% using exactly the same amounts of formalin and dimethylamine as in Example 1. Furthermore dimethyl sulfate
34.8g (0.276 mole to 100 mole% dimethylamine)
The quaternization reaction was carried out using the method disclosed in JP-A-57-67601, and the concentration was 10%, pH 5.0, viscosity
6200cps, total cation equivalent (measured at PH3.0)
1.79meq/g, quaternary cation equivalent (measured at PH10.0)
A Mannitz quaternized product of 1.32 meq/g was obtained. Example 5 The following test was carried out for the purpose of comparison under so-called acidic papermaking conditions. Comparative example (1) above for bleached hardwood pulp with a water content of 450 c.c.
-(6) and the products of Examples (1) to (3) are added in an amount of 0.5 weight percent per absolute dry weight of pulp to the amount of paper stock adjusted to PH4.5 and PH5.5 using aluminum sulfate, Paper with a basis weight of 60 g/m 2 was made using a Tatsupi standard sheet machine as usual, and after pressurized dehydration and drying, the various strengths of the resulting dry paper sheets were measured according to the JIS and Tatsupi methods. The values shown in Tables 1 to 3 were obtained. The evaluation items and test methods are as shown below. Test items and test methods: - Bursting strength: JIS P-8112 Tensile strength: JIS P-8131 Internal strength: Tappi RC-308 Internal Bod Tester Surface strength: JIS p-8129 (IGT method) TV = 20, pendulum law
【表】【table】
【表】【table】
【表】
実施例 ６
いわゆる中性抄紙条件下に於ける評価を行なう
目的で、以下に述べる試験を実施した。
紙料のPH調整に硫酸もしくは硅酸ソーダーを用
いた以外は全て実施例５と全く同じ方法で、実施
例４の製品を添加・抄紙し、評価した結果、表−
４に示す値を得た。[Table] Example 6 The following test was conducted for the purpose of evaluation under so-called neutral papermaking conditions. The product of Example 4 was added and made into paper in the same manner as in Example 5, except that sulfuric acid or sodium silicate was used to adjust the pH of the paper stock. As a result of the evaluation, Table -
The values shown in 4 were obtained.
【表】
参考例 １
抄紙機のプレスロール脱水時に於けるプレスロ
ールからの湿紙の剥離性を測定する目的で以下に
示す試験を実施した。
水度230c.c.の新聞故紙パルプに、カチオンデ
ンプン、市販アニオン性ポリアクリルアミド、実
施例(1)及び(2)の製品を、硫酸アルミニウムでPH
4.5もしくはPH55に調整された紙料に対し、パル
プ絶乾重量当り、1.0重量％添加し、常法通りタ
ツピースタンダードシートマシンにて抄紙した。
抄紙後直ちに表面研摩されたステンレススチール
板（SUS−27）に紙の表面がステンレス板に接
触する様に貼り付け、湿紙の裏面に乾燥紙を１
枚当て、この状態で加圧脱水処理（30Kg／cm2×３
分間）をする。加圧開放後、裏当てに使用した
紙を取りはずし、次にステンレス板に貼り付いた
湿紙を一端からほぼ一定の速度で引き剥し、この
時ステンレス板に付着した紙カスを採取し、110
±５℃にて乾燥し、乾燥重量を求めた。この値が
高いもの程、プレスロールからの剥離性に劣るも
のとの判断材料とすることができる。以上の試験
の結果、表−５に示す値を得た。[Table] Reference Example 1 The following test was conducted for the purpose of measuring the releasability of wet paper from the press roll during dehydration of the press roll of a paper machine. Add cationic starch, commercially available anionic polyacrylamide, and the products of Examples (1) and (2) to waste newspaper pulp with a water content of 230 c.c. and PH with aluminum sulfate.
It was added in an amount of 1.0% by weight based on the absolute dry weight of the pulp to a paper stock adjusted to pH 4.5 or PH55, and paper was made using a Tatsupi standard sheet machine in the usual manner.
Immediately after making the paper, attach it to a polished stainless steel plate (SUS-27) so that the surface of the paper is in contact with the stainless steel plate, and place one layer of dry paper on the back of the wet paper.
Apply the sheet and pressurize dehydration in this state (30Kg/cm 2 × 3
minutes). After releasing the pressure, remove the paper used as the backing, then peel off the wet paper stuck to the stainless steel plate from one end at an almost constant speed, collect the paper scraps that stuck to the stainless steel plate at 110
It was dried at ±5°C and the dry weight was determined. The higher this value is, the worse the peelability from the press roll can be determined. As a result of the above tests, the values shown in Table 5 were obtained.
Claims (1)
ルー及び／又はメタアクリルーアミド系水溶性
樹脂成分（）との、重量比が（）：（）＝
80：20〜20：80である混合組成物、 もしくは (A)′ デンプン類からなる成分（）と上記樹脂
成分（）形成性単量体成分（）′との、重
量比が（）：（）′＝80：20〜20：80である
組成物を、中性乃至酸性条件下、水溶性ラジカ
ル触媒の存在下で水溶性樹脂形成条件下に重合
して得られた組成物 の、ホルムアルデヒド及び第２級アミン類による
マンニツヒ反応生成物であつて、そのカチオン当
量が0.3ミリ当量／ｇ以上であるマンニツヒ化生
成物、又はカチオン当量が0.2ミリ当量／ｇ以上
である該マンニツヒ化生成物の四級化物を有効成
分として含有することを特徴とする製紙用添加
剤。 ２ 該水溶性樹脂成分（）もしくはその形成性
単量体成分（）′が、下記(a)、(b)及び(c) (a) アクリルアミド及びメタアクリルアミドより
成る群からえらばれた少なくとも一種の酸アミ
ド基含有単量体、 (b) 上記(a)と共重合可能なエチレン系不飽和カル
ボン酸もしくはその塩類、 (c) 上記(a)及び／又は(b)と共重合可能な上記(a)及
び(b)以外のビニル系単量体 からみちびかれた水溶性樹脂成分（）もしくは
その形成性単量体成分（）′であつて、且つそ
の総モル数に対する角単量体のモル・パーセント
の比が、(a)：(b)：(c)＝100〜50：０〜50：０〜30
である特許請求の範囲第１項記載の製紙用添加
剤。 ３ (A) デンプン類からなる成分（）とアクリ
ル及び／又はメタアクリル−アミド系水溶性樹
脂成分（）との、重量比が（）：（）＝
80：20〜20：80である混合組成物、 もしくは (A)′ デンプン類からなる成分（）と上記樹脂
成分（）形成性単量体成分（）′との、重
量比が（）：（）′＝80：20〜20：80である
組成物を、中性乃至酸性条件下、水溶性ラジカ
ル触媒の存在下で水溶性樹脂形成条件下に重合
して得られた組成物 の、ホルムアルデヒド及び第２級アミン類による
マンニツヒ反応生成物であつて、そのカチオン当
量が0.3ミリ当量／ｇ以上であるマンニツヒ化生
成物、又はカチオン当量が0.2ミリ当量／ｇ以上
である該マンニツヒ化生成物の四級化物を、抄紙
機に送入する以前の任意の過程に於て、紙料原料
乃至調製紙料原料中に該原料中のパルプ乾燥重量
に基いて約0.01〜約５重量％配合し、PH約4.5〜
約10の条件下で抄造することを特徴とする製紙方
法。[Scope of Claims] 1 (A) The weight ratio of the starch component () and the acrylic and/or methacrylamide water-soluble resin component () is ():()=
A mixed composition having a ratio of 80:20 to 20:80, or (A)' a weight ratio of the starch component () and the resin component ()-forming monomer component ()';)' = 80:20 to 20:80 under neutral to acidic conditions in the presence of a water-soluble radical catalyst under water-soluble resin forming conditions. Mannitz reaction products with secondary amines, the cation equivalent of which is 0.3 meq/g or more, or the mannitz reaction product of which the cation equivalent is 0.2 meq/g or more A papermaking additive characterized by containing a graded product as an active ingredient. 2. The water-soluble resin component () or its forming monomer component ()' is at least one selected from the group consisting of the following (a), (b) and (c) (a) acrylamide and methacrylamide. Acid amide group-containing monomer, (b) Ethylenically unsaturated carboxylic acid or its salt copolymerizable with (a) above, (c) Above (a) copolymerizable with (a) and/or (b) above. A water-soluble resin component () or its forming monomer component ()′ derived from vinyl monomers other than a) and (b), and the mole of the square monomer relative to the total number of moles thereof.・The percentage ratio is (a):(b):(c)=100~50:0~50:0~30
The papermaking additive according to claim 1. 3 (A) The weight ratio of the starch component () and the acrylic and/or methacrylamide water-soluble resin component () is ():()=
A mixed composition having a ratio of 80:20 to 20:80, or (A)' a weight ratio of the starch component () and the resin component ()-forming monomer component ()';)' = 80:20 to 20:80 under neutral to acidic conditions in the presence of a water-soluble radical catalyst under water-soluble resin forming conditions. Mannitz reaction products with secondary amines, the cation equivalent of which is 0.3 meq/g or more, or the mannitz reaction product of which the cation equivalent is 0.2 meq/g or more The graded product is blended into the paper stock raw material or prepared paper stock raw material in an arbitrary process before being fed into the paper machine in an amount of about 0.01 to about 5% by weight based on the dry weight of the pulp in the raw material, and the PH Approximately 4.5~
A papermaking method characterized by papermaking under approximately 10 conditions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13294483A JPS6028599A (en) | 1983-07-22 | 1983-07-22 | Papermaking additive and method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13294483A JPS6028599A (en) | 1983-07-22 | 1983-07-22 | Papermaking additive and method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6028599A JPS6028599A (en) | 1985-02-13 |
| JPH0368157B2 true JPH0368157B2 (en) | 1991-10-25 |
Family
ID=15093143
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13294483A Granted JPS6028599A (en) | 1983-07-22 | 1983-07-22 | Papermaking additive and method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6028599A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2620806B2 (en) * | 1988-07-11 | 1997-06-18 | 星光化学工業株式会社 | Papermaking additives and papermaking methods |
| JPH0773744B2 (en) * | 1990-06-18 | 1995-08-09 | ワイケイケイ株式会社 | Processing equipment such as mold materials |
| JP2009035689A (en) * | 2007-08-03 | 2009-02-19 | Asahi Glass Co Ltd | Water repellent greaseproof agent composition, water repellent greaseproof paper, and its manufacturing method |
-
1983
- 1983-07-22 JP JP13294483A patent/JPS6028599A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6028599A (en) | 1985-02-13 |
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