JPH0140158B2 - - Google Patents
Info
- Publication number
- JPH0140158B2 JPH0140158B2 JP56211638A JP21163881A JPH0140158B2 JP H0140158 B2 JPH0140158 B2 JP H0140158B2 JP 56211638 A JP56211638 A JP 56211638A JP 21163881 A JP21163881 A JP 21163881A JP H0140158 B2 JPH0140158 B2 JP H0140158B2
- Authority
- JP
- Japan
- Prior art keywords
- pva
- modified pva
- vinyl acetate
- paper
- copolymer
- 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
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 24
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 23
- 239000000049 pigment Substances 0.000 claims description 18
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 16
- 239000008199 coating composition Substances 0.000 claims description 16
- 229920001577 copolymer Polymers 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- ULYOZOPEFCQZHH-UHFFFAOYSA-N n-(methoxymethyl)prop-2-enamide Chemical compound COCNC(=O)C=C ULYOZOPEFCQZHH-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- UTSYWKJYFPPRAP-UHFFFAOYSA-N n-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCNC(=O)C=C UTSYWKJYFPPRAP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000914 phenoxymethylpenicillanyl group Chemical group CC1(S[C@H]2N([C@H]1C(=O)*)C([C@H]2NC(COC2=CC=CC=C2)=O)=O)C 0.000 description 44
- 239000000123 paper Substances 0.000 description 21
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 16
- 238000007127 saponification reaction Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000011087 paperboard Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 229920001567 vinyl ester resin Polymers 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical group OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 239000005018 casein Substances 0.000 description 2
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 2
- 235000021240 caseins Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid group Chemical group C(\C=C/C(=O)O)(=O)O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011115 styrene butadiene Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- RSNDTPFSMDVWCS-UHFFFAOYSA-N 2-(butoxymethyl)prop-2-enamide Chemical compound CCCCOCC(=C)C(N)=O RSNDTPFSMDVWCS-UHFFFAOYSA-N 0.000 description 1
- TWYISXLZCIVDDW-UHFFFAOYSA-N 2-methyl-n-(2-methylpropoxymethyl)prop-2-enamide Chemical compound CC(C)COCNC(=O)C(C)=C TWYISXLZCIVDDW-UHFFFAOYSA-N 0.000 description 1
- OAKRGDFNVFVVMD-UHFFFAOYSA-N 2-methyl-n-(propan-2-yloxymethyl)prop-2-enamide Chemical compound CC(C)OCNC(=O)C(C)=C OAKRGDFNVFVVMD-UHFFFAOYSA-N 0.000 description 1
- NYGLFZZNGBYARC-UHFFFAOYSA-N 2-methyl-n-(propoxymethyl)prop-2-enamide Chemical compound CCCOCNC(=O)C(C)=C NYGLFZZNGBYARC-UHFFFAOYSA-N 0.000 description 1
- ZBVNHRJWNBTZFH-UHFFFAOYSA-N 2-methyl-n-[(2-methylpropan-2-yl)oxymethyl]prop-2-enamide Chemical compound CC(=C)C(=O)NCOC(C)(C)C ZBVNHRJWNBTZFH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- -1 acrylic ester Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- HDERJYVLTPVNRI-UHFFFAOYSA-N ethene;ethenyl acetate Chemical group C=C.CC(=O)OC=C HDERJYVLTPVNRI-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 125000000686 lactone group Chemical group 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- KCTMTGOHHMRJHZ-UHFFFAOYSA-N n-(2-methylpropoxymethyl)prop-2-enamide Chemical compound CC(C)COCNC(=O)C=C KCTMTGOHHMRJHZ-UHFFFAOYSA-N 0.000 description 1
- ADGJZVKOKVENDN-UHFFFAOYSA-N n-(butoxymethyl)-2-methylprop-2-enamide Chemical compound CCCCOCNC(=O)C(C)=C ADGJZVKOKVENDN-UHFFFAOYSA-N 0.000 description 1
- YGRMNBNGHHDGCX-UHFFFAOYSA-N n-(ethoxymethyl)-2-methylprop-2-enamide Chemical compound CCOCNC(=O)C(C)=C YGRMNBNGHHDGCX-UHFFFAOYSA-N 0.000 description 1
- LSWADWIFYOAQRZ-UHFFFAOYSA-N n-(ethoxymethyl)prop-2-enamide Chemical compound CCOCNC(=O)C=C LSWADWIFYOAQRZ-UHFFFAOYSA-N 0.000 description 1
- YOZHLACIXDCHPV-UHFFFAOYSA-N n-(methoxymethyl)-2-methylprop-2-enamide Chemical compound COCNC(=O)C(C)=C YOZHLACIXDCHPV-UHFFFAOYSA-N 0.000 description 1
- IFMYKAUQEUJSKT-UHFFFAOYSA-N n-(propan-2-yloxymethyl)prop-2-enamide Chemical compound CC(C)OCNC(=O)C=C IFMYKAUQEUJSKT-UHFFFAOYSA-N 0.000 description 1
- XTMDYDPHCFUVKQ-UHFFFAOYSA-N n-(propoxymethyl)prop-2-enamide Chemical compound CCCOCNC(=O)C=C XTMDYDPHCFUVKQ-UHFFFAOYSA-N 0.000 description 1
- JLOVAZFUZOTELM-UHFFFAOYSA-N n-[(2-methylpropan-2-yl)oxymethyl]prop-2-enamide Chemical compound CC(C)(C)OCNC(=O)C=C JLOVAZFUZOTELM-UHFFFAOYSA-N 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000013053 water resistant agent Substances 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Paper (AREA)
Description
本発明は紙用顔料コーテイング組成物に関す
る。更に詳しくは分子内に下式（）
（ここで、R1は水素原子または低級アルキル基、
R2はアルキル基を各々意味する。）
で示される架橋性能を有する共重合単位を含む変
性ポリビニルアルコールと顔料とを含有せしめた
塗工性に優れ、かつ紙あるいは板紙（以下、両者
を総称して紙と呼ぶ）に塗工することにより耐水
性や強度などの優れた物性を有する塗工紙を与え
る、紙用顔料コーテイング組成物に関する。
従来より顔料コーテイング用の結合剤としては
カゼイン、殿粉、ポリビニルアルコール（以下
PVAと略記する）あるいはスチレン−ブタジエ
ンラテツクスなどのラテツクス類が用いられてい
る。このうち、PVAは他の結合剤と比較して塗
工紙の表面強度、印刷適性などの点で優れた性能
を有している反面、耐水性に乏しいために何らか
の耐水化処理が必要とされているが、従来の耐水
化剤の併用はその効果が充分でないと同時に塗工
液の粘度が高くなり易く塗工性においてしばしば
不都合が生じていた。粘度を低下させ塗工性を改
良する目的をもつてPVAの重合度を低下させる
時は、これを用いた塗工紙の表面強度や印刷適性
の性能もまた低下するため本質的な改質法とはな
り得ない。
以上のような紙用コーテイング剤として求めら
れる塗工性、耐水性あるいは印刷適性を改善、改
良することを目的としてPVA系結合剤において
もこれまでにも多くの共重合変性PVAが提案さ
れている。例えば、カルボキシル基を導入した変
性PVAについては特公昭44−5331号公報、特公
昭46−7606号公報、特公昭53−35611号公報など
に記載されており、アクリルアミドを共重合変性
したPVAについては特公昭46−7605号公報、特
公昭46−26407号公報、特公昭47−42724号公報な
どに記載され、またラクトン環を導入した変性
PVAについては特公昭52−39442号公報などに記
載されている。これらのうち、カルボキシル基変
性PVAなどはこれを結合剤として用いた時、高
濃度顔料塗工液における流動性についてはある程
度改善されてはいるが、顔料結合力は充分ではな
くまた、耐水性についてはほとんど改良が見られ
ていない。こうして、PVA系結合剤において、
塗工性、耐水性、塗工紙物性の三者を満足させる
方法は未だ完成されていないのが現状である。
本発明者らはかかる問題点の解決を目的として
PVAの化学変性に関してより広範囲に検討を行
い、得られた多数の変性PVAを結合剤として用
いて顔料コーテイングを実施し、その結合剤とし
ての評価を実施した結果、分子内に前記の架橋性
基を含む変性PVAを使用した時は、塗工性に優
れると同時に塗工紙の表面強度あるいは印刷適性
に優れ、更に耐水性が著しく改良されることを見
出して本発明を完成するに至つた。
本発明の顔料コーテイング組成物において用い
られるバインダーとしての変性PVAは、ビニル
エステル、とりわけ酢酸ビニルと式
CH2＝CR1−CONHCH2O−R2（R1は水素原子ま
たは低級アルキル基、R2はアルキル基）で表わ
される単量体、とりわけR1が水素原子またはメ
チル基、R2が炭素数１〜４のアルキル基である
Ｎ−アルコキシメチル（メタ）アクリルアミド、
特に好ましくはＮ−メトキシメチルアクリルアミ
ドまたはＮ−ｎ−ブトキシメチルアクリルアミド
とをラジカル重合開始剤を用いて共重合させ、し
かる後にこの共重合体のアルコール溶液にアルカ
リ触媒を作用させて共重合体中のビニルエステル
単位を部分的にあるいは高度にケン化せしめ、ビ
ニルアルコール単位とすることにより製造され
る。
前述の共重合体を製造する際に使用し得るビニ
ルエステルは共重合後ケン化をすればビニルアル
コールとなることから任意のビニルエステルで本
質的には同一の効果を有する経済的にみて酢酸ビ
ニルが好ましい。
前述した式CH2＝CR1−CONHCH2O−R2（R1
は水素原子または低級アルキル基、R2はアルキ
ル基）で表わされる単量体の具体的な例はＮ−メ
トキシメチルアクリルアミド、Ｎ−メトキシメチ
ルメタクリルアミド、Ｎ−エトキシメチルアクリ
ルアミド、Ｎ−エトキシメチルメタクリルアミ
ド、Ｎ−ｎ−プロポキシメチルアクリルアミド、
Ｎ−ｎ−プロポキシメチルメタクリルアミド、Ｎ
−イソプロポキシメチルアクリルアミド、Ｎ−イ
ソプロポキシメチルメタクリルアミド、Ｎ−ｎ−
ブトキシメチルアクリルアミド、Ｎ−ｎ−ブトキ
シメチルメタクリルアミド、Ｎ−イソブトキシメ
チルアクリルアミド、Ｎ−イソブトキシメチルメ
タクリルアミド、Ｎ−tert−ブトキシメチルアク
リルアミド、Ｎ−tert−ブトキシメチルメタクリ
ルアミドが挙げられ、このうちＮ−メトキシメチ
ルアクリルアミドあるいはＮ−ｎ−ブトキシメチ
ルアクリルアミドが効果と経済性の点で特に好ま
しい。これらの単量体は従来からもよく知られて
おり、例えば英国特許955420号においては酢酸ビ
ニルおよびアクリル酸エステルとの共重合体につ
いて示されているが、Ｎ−アルコキシメチル（メ
タ）アクリルアミドとビニルエステルとの共重合
体をケン化することにより生成した共重合体ケン
化物及びその有用性については知られていない。
上述したＮ−アルコキシメチル（メタ）アクリ
ルアミドとビニルエステルとの共重合体のケン化
物及びその具体的製造方法については本発明者等
によつて開発され、すでに特願昭56−176024号
（特開昭58−76403号公報参照）および特願昭56−
178594号（特開昭58−80304号公報参照）として
特許出願されているが、本発明の目的に対して用
いられる上記変性PVAとしては通常Ｎ−アルコ
キシメチル（メタ）アクリルアミド単位の含量が
0.05〜10モル％、ケン化度70モル％以上のものが
用いられる。
また本発明の紙用顔料コーテイング組成物に用
いられる顔料としては、クレー、カオリン、炭酸
カルシウム、チタン白、ケイ酸アルミニウム、サ
チン白などが用いられる。これらの顔料の分散剤
としてピロリン酸ナトリウム、ヘキサメタリン酸
ナトリウム、ポリアクリル酸ナトリウムなどを使
用することは従来通りである。本発明の組成物に
おいては結合剤として本発明に示された架橋性基
を有する変性PVAを単独で使用することによつ
て塗工性が優れると同時に耐水性などの品質に優
れた塗工紙を得ることができるものであるが、組
成物のPHをできるだけ低下させた方が耐水性が高
くなる傾向があり、また必要に応じて塩化アンモ
ニウム、硫酸アンモニウム、硝酸アンモニウムな
どの架橋助剤あるいは他の結合剤、たとえば殿
粉、変性殿粉、カゼイン、PVA、カルボキシル
基変性PVA、アクリルアミド変性PVA、スルホ
ン基変性PVA、カチオン基変性PVA等の変性
PVA、あるいは合成樹脂エマルジヨン（スチレ
ン−ブタジエンラテツクス、ポリアクリル酸エス
テルエマルジヨン、酢酸ビニル−エチレン共重合
エマルジヨン、酢酸ビニル−アクリル酸エステル
共重合エマルジヨンなど）を併用することもでき
る。また、必要に応じて、消泡剤などの添加剤、
あるいははグリオキザール、尿素樹脂、メラミン
樹脂、多価金属塩、水溶性ポリアミド樹脂などの
耐水化剤を添加併用することもできる。本発明の
組成物において変性PVAは顔料100部に対して通
常３〜10部使用され、塗工液の固形分濃度は30〜
63％の範囲から選択するのが適当である。塗工液
は、エアナイフコーター、ブレードコーター、ロ
ールコーター、サイズプレスコーターなどの公知
のコーターを用いて紙面に塗工され、乾燥工程で
乾燥した後スーパーカレンダーを通して仕上げら
れる。塗工量は目的により広範囲となり特に制限
はないが、固形分で0.1〜30ｇ／m2程度が通常採
用される。以下、実施例により本発明の顔料コー
テイング組成物につき説明する。以下、部又は％
とあるのは特に断りのない限り、重量基準を示し
ている。又cpは粘度のセンチポイズを示す。
実施例 １
（洋紙に対する塗工例）
ヘキサメタリン酸ナトリウム0.5部を溶解した
水溶液47.5部を激しく撹拌しながらカオリンクレ
ー100部を加えて均一に分散させ、しかる後に該
分散液を、Ｎ−メトキシメチルアクリルアミド単
位を２モル％含有し、酢酸ビニル単位のケン化度
が98.5モル％、平均重合度が630の変性PVAの20
％水溶液30部に添加混合して、固形分濃度60％、
30℃における粘度が3030cpのコーテイング組成
物を調製した。このコーテイング組成物を試験用
フレキシブルブレードコーターを用いて上質紙原
紙（秤量60ｇ／m2）に固形分塗工量が15ｇ／m2と
なるごとく塗工した後105℃で２分間乾燥後表面
温度85℃、線圧100Kg／cmの条件下にカレンダー
仕上げを行なつた。得られた塗工紙を20℃、65％
RHで72時間調湿後その性能を評価した。結果を
第１表に示した。
比較例 １〜３
実施例１の変性PVAに代えて次のPVAあるい
は変性PVAを使用した他は実施例１と同様にし
て性能評価を実施した。結果を第１表に合わせて
示す。
比較例１において使用したPVA：
ケン化度98.5モル％、平均重合度が630の
PVA。
比較例２において使用した変性PVA：
マレイン酸モノメチルと酢酸ビニルとの共重合
体をケン化して得た、マレイン酸単位を２モル％
含有し、酢酸ビニル単位のケン化度が98.6モル
％、平均重合度が640の変性PVA。
比較例３において使用した変性PVA：
アクリルアミドと酢酸ビニルとの共重合体をケ
ン化して得た、アクリルアミド単位を２モル％含
有し、酢酸ビニル単位のケン化度が99.0モル％、
平均重合度が650の変性PVA。
第１表より、本発明のコーテイング組成物を使
用した塗工紙は表面強度、白色度、光沢度、印刷
適性において極めて高い物性を与えることが明ら
かである。
The present invention relates to pigment coating compositions for paper. For more details, use the following formula () in the molecule. (Here, R 1 is a hydrogen atom or a lower alkyl group,
Each R 2 represents an alkyl group. ) Contains a pigment and a modified polyvinyl alcohol containing a copolymerized unit with crosslinking performance as shown in the following, and has excellent coating properties and can be applied to paper or paperboard (hereinafter, both are collectively referred to as paper). The present invention relates to a pigment coating composition for paper that provides coated paper with excellent physical properties such as water resistance and strength. Traditionally, binders for pigment coatings include casein, starch, and polyvinyl alcohol (hereinafter referred to as
Latexes such as PVA (abbreviated as PVA) or styrene-butadiene latex are used. Among these, PVA has superior performance in terms of surface strength and printability of coated paper compared to other binders, but on the other hand, it has poor water resistance and requires some kind of water resistance treatment. However, the combined use of conventional waterproofing agents has not only been insufficiently effective, but also tends to increase the viscosity of the coating solution, often causing problems in coating properties. When lowering the degree of polymerization of PVA for the purpose of lowering viscosity and improving coating properties, the surface strength and printability of the coated paper using this also decreases, so it is not an essential modification method. It cannot be. Many copolymerized PVAs have been proposed as PVA binders for the purpose of improving the coatability, water resistance, or printability required for paper coating agents as described above. . For example, modified PVA into which a carboxyl group has been introduced is described in Japanese Patent Publication No. 44-5331, Japanese Patent Publication No. 7606-1976, Japanese Patent Publication No. 35611-1973, etc., and PVA modified by copolymerization of acrylamide is described. Modifications that are described in Japanese Patent Publication No. 46-7605, Japanese Patent Publication No. 46-26407, Japanese Patent Publication No. 47-42724, etc., and in which a lactone ring is introduced
PVA is described in Japanese Patent Publication No. 52-39442. Among these, when carboxyl group-modified PVA is used as a binder, the fluidity in high-concentration pigment coating liquids is improved to some extent, but the pigment binding strength is not sufficient and the water resistance is has seen almost no improvement. In this way, in the PVA-based binder,
At present, a method that satisfies the three requirements of coatability, water resistance, and coated paper properties has not yet been perfected. The present inventors aimed to solve such problems.
We conducted a more extensive study on the chemical modification of PVA, performed pigment coating using a large number of the obtained modified PVA as a binder, and evaluated its use as a binder. The present invention was completed based on the discovery that when modified PVA containing . The modified PVA used as binder in the pigment coating composition of the invention is a vinyl ester, in particular vinyl acetate, having the formula CH2 = CR1 - CONHCH2O - R2 , where R1 is a hydrogen atom or a lower alkyl group, R2 is an alkyl group), especially N-alkoxymethyl (meth)acrylamide, in which R 1 is a hydrogen atom or a methyl group, and R 2 is an alkyl group having 1 to 4 carbon atoms;
Particularly preferably, N-methoxymethylacrylamide or N-n-butoxymethylacrylamide is copolymerized using a radical polymerization initiator, and then an alkaline catalyst is applied to an alcohol solution of the copolymer to form a copolymer. It is produced by partially or highly saponifying vinyl ester units to convert them into vinyl alcohol units. Vinyl esters that can be used in the production of the above-mentioned copolymers can be converted into vinyl alcohol by saponification after copolymerization, so any vinyl ester can be used economically as vinyl acetate, which has essentially the same effect. is preferred. The above formula CH 2 = CR 1 −CONHCH 2 O−R 2 (R 1
is a hydrogen atom or a lower alkyl group, and R2 is an alkyl group) Specific examples of the monomer are N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-ethoxymethylmethacryl amide, N-n-propoxymethylacrylamide,
N-n-propoxymethyl methacrylamide, N
-isopropoxymethylacrylamide, N-isopropoxymethylmethacrylamide, N-n-
Examples include butoxymethylacrylamide, N-n-butoxymethylmethacrylamide, N-isobutoxymethylacrylamide, N-isobutoxymethylmethacrylamide, N-tert-butoxymethylacrylamide, and N-tert-butoxymethylmethacrylamide. N-methoxymethylacrylamide or N-n-butoxymethylacrylamide is particularly preferred in terms of effectiveness and economy. These monomers have long been well known; for example, in British Patent No. 955420, a copolymer with vinyl acetate and an acrylic ester is shown, but a copolymer with N-alkoxymethyl (meth)acrylamide and vinyl A saponified copolymer produced by saponifying a copolymer with an ester and its usefulness are not known. The saponified product of the copolymer of N-alkoxymethyl (meth)acrylamide and vinyl ester mentioned above and its specific production method have been developed by the present inventors and have already been disclosed in Japanese Patent Application No. 176024/1989 (Refer to Publication No. 76403, 1982) and patent application 1982.
Although a patent application has been filed as No. 178594 (see JP-A-58-80304), the modified PVA used for the purpose of the present invention usually has a content of N-alkoxymethyl (meth)acrylamide units.
Those with a saponification degree of 0.05 to 10 mol% and a saponification degree of 70 mol% or more are used. Further, as the pigment used in the paper pigment coating composition of the present invention, clay, kaolin, calcium carbonate, titanium white, aluminum silicate, satin white, etc. are used. It is conventional to use sodium pyrophosphate, sodium hexametaphosphate, sodium polyacrylate, etc. as a dispersant for these pigments. In the composition of the present invention, by using modified PVA having the crosslinkable group shown in the present invention alone as a binder, coated paper with excellent coatability and quality such as water resistance can be obtained. However, water resistance tends to be higher when the pH of the composition is lowered as much as possible. modified agents, such as starch, modified starch, casein, PVA, carboxyl group-modified PVA, acrylamide-modified PVA, sulfone group-modified PVA, cationic group-modified PVA, etc.
PVA or a synthetic resin emulsion (styrene-butadiene latex, polyacrylate emulsion, vinyl acetate-ethylene copolymer emulsion, vinyl acetate-acrylate copolymer emulsion, etc.) can also be used in combination. In addition, additives such as antifoaming agents,
Alternatively, a water resistant agent such as glyoxal, urea resin, melamine resin, polyvalent metal salt, water-soluble polyamide resin, etc. may be added and used in combination. In the composition of the present invention, modified PVA is usually used in an amount of 3 to 10 parts per 100 parts of pigment, and the solid content concentration of the coating liquid is 30 to 10 parts.
It is appropriate to select from the range of 63%. The coating liquid is applied to the paper surface using a known coater such as an air knife coater, blade coater, roll coater, or size press coater, and after drying in a drying process, it is finished by passing through a super calendar. The coating amount varies widely depending on the purpose and is not particularly limited, but a solid content of about 0.1 to 30 g/m 2 is usually employed. The pigment coating composition of the present invention will be explained below with reference to Examples. Hereinafter, parts or %
Unless otherwise specified, "" indicates the weight standard. Also, cp indicates viscosity centipoise. Example 1 (Example of coating on Western paper) 100 parts of kaolin clay was added to 47.5 parts of an aqueous solution in which 0.5 parts of sodium hexametaphosphate was dissolved while stirring vigorously to uniformly disperse the solution, and then the dispersion was mixed with N-methoxymethylacrylamide. 20 of modified PVA containing 2 mol% of vinyl acetate units, a degree of saponification of vinyl acetate units of 98.5 mol%, and an average degree of polymerization of 630.
% aqueous solution and mix to obtain a solid concentration of 60%.
A coating composition was prepared with a viscosity of 3030 cp at 30°C. This coating composition was applied to a high-quality base paper (weighing 60 g/m 2 ) using a test flexible blade coater so that the solid content coating amount was 15 g/m 2 , and after drying at 105°C for 2 minutes, the surface temperature Calender finishing was carried out under the conditions of 85°C and a linear pressure of 100 kg/cm. The obtained coated paper was heated to 20℃ and 65%
Its performance was evaluated after humidity conditioning at RH for 72 hours. The results are shown in Table 1. Comparative Examples 1 to 3 Performance evaluation was performed in the same manner as in Example 1, except that the following PVA or modified PVA was used in place of the modified PVA in Example 1. The results are also shown in Table 1. PVA used in Comparative Example 1: Saponification degree of 98.5 mol%, average polymerization degree of 630.
PVA. Modified PVA used in Comparative Example 2: 2 mol% of maleic acid units obtained by saponifying a copolymer of monomethyl maleate and vinyl acetate.
modified PVA with a saponification degree of vinyl acetate units of 98.6 mol% and an average degree of polymerization of 640. Modified PVA used in Comparative Example 3: Contains 2 mol% of acrylamide units, obtained by saponifying a copolymer of acrylamide and vinyl acetate, and has a degree of saponification of vinyl acetate units of 99.0 mol%.
Modified PVA with an average degree of polymerization of 650. From Table 1, it is clear that the coated paper using the coating composition of the present invention provides extremely high physical properties in terms of surface strength, whiteness, gloss, and printability.
【表】
実施例 ２〜６
実施例１の変性PVAに代えて、第２表に示す
変性PVAを使用した他は実施例１と同様にして
顔料コーテイング組成物を調製し、各々を塗工し
た塗工紙について物性評価を実施した。結果を第
３表に示した。[Table] Examples 2 to 6 Pigment coating compositions were prepared in the same manner as in Example 1, except that the modified PVA shown in Table 2 was used in place of the modified PVA in Example 1, and each was applied. The physical properties of the coated paper were evaluated. The results are shown in Table 3.
【表】【table】
【表】
実施例 ７
（白板紙に対する塗工例）
ヘキサメタリン酸ナトリウム0.5部を溶解した
水溶液63.5部を激しく撹拌しながらカオリンクレ
ー100部を加えて均一に分散させ、しかる後に該
分散液を、Ｎ−メトキシメチルアクリルアミド単
位を2.0モル％含有し、酢酸ビニル単位のケン化
度が98モル％、平均重合度が1630である変性
PVAの８％水溶液75部に添加混合し、更にスチ
レン−ブタジエン共重合体ラテツクス（JSR−
0692、固形分49％）20.4部を混合撹忰して、固形
分濃度45％、30℃における粘度が650cpのコーテ
イング組成物を調製した。また、このコーテイン
グ組成物を塗工液として白板紙原紙（秤量280
ｇ／m2）に対しエアーナイフコーターを使用して
固形分塗工量が15ｇ／m2となるよう塗工し、150
℃の熱風乾燥炉中を通過させた後、カレンダー仕
上げを実施した。得られた塗工白板紙を20℃、65
％R.H.で72時間調湿後その性能を評価した。結
果を第４表に示す。
比較例 ４〜６
実施例７の変性PVAに代えて次のPVAあるい
は変性PVAを使用した他は実施例10と同様にし
て性能評価を実施した。結果を第４表に合わせて
示す。
比較例４において使用したPVA：
ケン化度99モル％、平均重合度が1640のPVA。
比較例５において使用した変性PVA：
マレイン酸モノメチルと酢酸ビニルとの共重合
体をケン化して得た、マレイン酸単位を２モル％
含有し、酢酸ビニル単位のケン化度が98.5モル
％、平均重合度が1650の変性PVA。
比較例６において使用した変性PVA：
アクリルアミドと酢酸ビニルとの共重合体をケ
ン化して得た、アクリルアミド単位を２モル％含
有し、酢酸ビニル単位のケン化度が98.9モル％、
平均重合度が1660の変性PVA。
第４表より明らかな如く、本発明のコーテイン
グ組成物は耐水性が顕著に高いことが特色で、更
にこれを使用した塗工紙は表面強度、白色度、光
沢度、印刷適性およびインク受理性が優れた物性
を有していることが確認された。[Table] Example 7 (Coating example for white paperboard) 100 parts of kaolin clay was added to 63.5 parts of an aqueous solution in which 0.5 part of sodium hexametaphosphate was dissolved with vigorous stirring, and the mixture was uniformly dispersed. - Modification containing 2.0 mol% of methoxymethylacrylamide units, a degree of saponification of vinyl acetate units of 98 mol%, and an average degree of polymerization of 1630
Add and mix to 75 parts of an 8% aqueous solution of PVA, and then make a styrene-butadiene copolymer latex (JSR-
0692 (solid content 49%) were mixed and stirred to prepare a coating composition having a solid content concentration of 45% and a viscosity of 650 cp at 30°C. In addition, this coating composition was used as a coating liquid on white paperboard base paper (basis weight 280
g/m 2 ) using an air knife coater so that the solid content coating amount is 15 g/m 2 .
After passing through a hot air drying oven at ℃, calender finishing was performed. The resulting coated white paperboard was heated at 20℃ and 65℃.
The performance was evaluated after humidity conditioning at %RH for 72 hours. The results are shown in Table 4. Comparative Examples 4 to 6 Performance evaluation was carried out in the same manner as in Example 10, except that the following PVA or modified PVA was used in place of the modified PVA of Example 7. The results are also shown in Table 4. PVA used in Comparative Example 4: PVA with a degree of saponification of 99 mol% and an average degree of polymerization of 1640. Modified PVA used in Comparative Example 5: 2 mol% of maleic acid units obtained by saponifying a copolymer of monomethyl maleate and vinyl acetate.
modified PVA with a saponification degree of vinyl acetate units of 98.5 mol% and an average degree of polymerization of 1650. Modified PVA used in Comparative Example 6: Contains 2 mol% of acrylamide units, obtained by saponifying a copolymer of acrylamide and vinyl acetate, and has a degree of saponification of vinyl acetate units of 98.9 mol%.
Modified PVA with an average degree of polymerization of 1660. As is clear from Table 4, the coating composition of the present invention is characterized by extremely high water resistance, and the coated paper using the same has excellent surface strength, whiteness, gloss, printability, and ink receptivity. was confirmed to have excellent physical properties.
【表】【table】
【表】
実施例 ８〜12
実施例７の変性PVAに代えて、第５表に示す。
変性PVAを使用した他は実施例７と同様にして
コーテイング組成物を調製し、この耐水性および
これを白板紙原紙に塗工した塗工紙について物性
評価を実施した。結果を第６表に示した。[Table] Examples 8 to 12 The modified PVA of Example 7 was replaced with those shown in Table 5.
A coating composition was prepared in the same manner as in Example 7 except that modified PVA was used, and the water resistance and physical properties of the coated paper obtained by coating white paperboard base paper were evaluated. The results are shown in Table 6.
【表】【table】
Claims (1)
単位を含む変性ポリビニルアルコールと顔料とを
含有する紙用顔料コーテイング組成物。 （ここで、R1は水素原子または低級アルキル基、
R2はアルキル基を各々意味する。） ２ 変性ポリビニルアルコールが、Ｎ−メトキシ
メチルアクリルアミドと酢酸ビニルとの共重合体
のケン化物である特許請求の範囲第１項に記載の
紙用顔料コーテイング組成物。 ３ 変性ポリビニルアルコールが、Ｎ−ｎ−ブト
キシメチルアクリルアミドと酢酸ビニルとの共重
合体のケン化物である特許請求の範囲第１項に記
載の紙用顔料コーテイング組成物。[Scope of Claims] 1. A pigment coating composition for paper containing a pigment and a modified polyvinyl alcohol containing a copolymerized unit represented by the following general formula () in the molecule. (Here, R 1 is a hydrogen atom or a lower alkyl group,
Each R 2 represents an alkyl group. 2. The paper pigment coating composition according to claim 1, wherein the modified polyvinyl alcohol is a saponified product of a copolymer of N-methoxymethylacrylamide and vinyl acetate. 3. The paper pigment coating composition according to claim 1, wherein the modified polyvinyl alcohol is a saponified product of a copolymer of N-n-butoxymethylacrylamide and vinyl acetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21163881A JPS58115194A (en) | 1981-12-29 | 1981-12-29 | Pigment coating composition for paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21163881A JPS58115194A (en) | 1981-12-29 | 1981-12-29 | Pigment coating composition for paper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58115194A JPS58115194A (en) | 1983-07-08 |
| JPH0140158B2 true JPH0140158B2 (en) | 1989-08-25 |
Family
ID=16609084
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21163881A Granted JPS58115194A (en) | 1981-12-29 | 1981-12-29 | Pigment coating composition for paper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58115194A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4818783A (en) * | 1986-11-07 | 1989-04-04 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Method for production of aqueous dispersion of inorganic pigment |
-
1981
- 1981-12-29 JP JP21163881A patent/JPS58115194A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58115194A (en) | 1983-07-08 |
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