JPS63162275A - Sheet for ink jet recording - Google Patents
Sheet for ink jet recordingInfo
- Publication number
- JPS63162275A JPS63162275A JP61311737A JP31173786A JPS63162275A JP S63162275 A JPS63162275 A JP S63162275A JP 61311737 A JP61311737 A JP 61311737A JP 31173786 A JP31173786 A JP 31173786A JP S63162275 A JPS63162275 A JP S63162275A
- Authority
- JP
- Japan
- Prior art keywords
- cationic
- recording
- color
- cationic polymer
- polymer
- 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.)
- Granted
Links
- 229920006317 cationic polymer Polymers 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 23
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- 150000001412 amines Chemical class 0.000 claims abstract description 5
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 8
- 150000003973 alkyl amines Chemical class 0.000 claims description 3
- 238000001454 recorded image Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 16
- 239000000049 pigment Substances 0.000 abstract description 11
- 230000000740 bleeding effect Effects 0.000 abstract description 9
- 239000011230 binding agent Substances 0.000 abstract description 7
- 239000000654 additive Substances 0.000 abstract description 6
- 229920001577 copolymer Polymers 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 5
- 150000001242 acetic acid derivatives Chemical class 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 abstract 1
- 125000003282 alkyl amino group Chemical group 0.000 abstract 1
- 125000003277 amino group Chemical group 0.000 abstract 1
- 239000011268 mixed slurry Substances 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 30
- 239000003086 colorant Substances 0.000 description 18
- -1 polyallylamine Chemical class 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 239000000243 solution Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000975 dye Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000011247 coating layer Substances 0.000 description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002736 nonionic surfactant Substances 0.000 description 5
- 239000002492 water-soluble polymer binding agent Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 3
- 229920000298 Cellophane Polymers 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 3
- 239000012190 activator Substances 0.000 description 3
- 239000002280 amphoteric surfactant Substances 0.000 description 3
- 229960003237 betaine Drugs 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 235000019646 color tone Nutrition 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 2
- LTMQZVLXCLQPCT-UHFFFAOYSA-N 1,1,6-trimethyltetralin Chemical compound C1CCC(C)(C)C=2C1=CC(C)=CC=2 LTMQZVLXCLQPCT-UHFFFAOYSA-N 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- SJEYSFABYSGQBG-UHFFFAOYSA-M Patent blue Chemical compound [Na+].C1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)S([O-])(=O)=O)S([O-])(=O)=O)=C1C=CC(=[N+](CC)CC)C=C1 SJEYSFABYSGQBG-UHFFFAOYSA-M 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000980 acid dye Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000982 direct dye Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000001254 oxidized starch Substances 0.000 description 2
- 235000013808 oxidized starch Nutrition 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- FPVVYTCTZKCSOJ-UHFFFAOYSA-N Ethylene glycol distearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCOC(=O)CCCCCCCCCCCCCCCCC FPVVYTCTZKCSOJ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- ZXFQDPHJZVBMJZ-UHFFFAOYSA-N OCC[N+]1(CC([O-])=O)CCN=C1 Chemical compound OCC[N+]1(CC([O-])=O)CCN=C1 ZXFQDPHJZVBMJZ-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- 229920002518 Polyallylamine hydrochloride Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 239000004147 Sorbitan trioleate Substances 0.000 description 1
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- 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 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical class C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- YQEMORVAKMFKLG-UHFFFAOYSA-N glycerine monostearate Natural products CCCCCCCCCCCCCCCCCC(=O)OC(CO)CO YQEMORVAKMFKLG-UHFFFAOYSA-N 0.000 description 1
- SVUQHVRAGMNPLW-UHFFFAOYSA-N glycerol monostearate Natural products CCCCCCCCCCCCCCCCC(=O)OCC(O)CO SVUQHVRAGMNPLW-UHFFFAOYSA-N 0.000 description 1
- 229940100608 glycol distearate Drugs 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 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 1
- 208000019423 liver disease Diseases 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5245—Macromolecular coatings characterised by the use of polymers containing cationic or anionic groups, e.g. mordants
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野〕
本発明はインクジェットプリンタの記録用シートに関す
るものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a recording sheet for an inkjet printer.
一般にインクジェット記録は直径数十ミクロンの細孔か
らインクを加圧噴出させ、生成したインク微粒子により
記録紙上にドツト記録を行う方式である。細孔からの安
定なインク噴出を確保する必要上通常の印刷インクのよ
うにインク中に、顔料、樹脂等を含有させることが困難
であり、一般に直接染料や酸性染料等の水溶性染料から
なる低粘度の水性インクが用いられる。このためインク
ジェット記録は記録濃度、光沢、耐光性、耐水性等の艷
録品質が一般の印刷に比べ見劣りするのが当然と考えら
れていた。Generally, inkjet recording is a method in which ink is ejected under pressure from pores with a diameter of several tens of microns, and dots are recorded on recording paper using the generated ink particles. Due to the need to ensure stable ink ejection from the pores, it is difficult to incorporate pigments, resins, etc. into the ink like normal printing inks, and it is generally made of water-soluble dyes such as direct dyes and acid dyes. A low viscosity water-based ink is used. For this reason, it has been considered natural that inkjet recording is inferior in recording quality such as recording density, gloss, light resistance, and water resistance compared to general printing.
しかしインクジェット記録方式の使用分野の拡大並びに
カラープリンタの普及につれて記録時の性能即ち、解像
度、濃度、カラー色調のあざやかさなどは勿論のこと、
記録後の耐水性、耐光性等の保存性も要求されるように
なった。However, as the field of use of the inkjet recording method expands and color printers become popular, recording performance, such as resolution, density, and vividness of color tones, has of course improved.
Preservability such as water resistance and light resistance after recording is also required.
このうち記録の解像度、濃度、カラー色調のあざやかさ
の対策としては、特開昭５５−５１５８３．同５６−１
４８５８３ 、及び同５６−１４８５８５公報などでし
シリカ系顔料と水溶性高分子バインダーからなる塗料を
１０８／ｒｎ’以上支持体に塗布することが提案されて
おり、更に本発明者等は、特開昭５９−１８５６９０に
おいて支持体上に粒度分布（Ｒｏｓｉｎ−Ｒａｍｍｌｅ
ｒ分布）の均等数１６月、１０以上でありかつＢＥＴ法
による比表面積２００ ｔｎ’／ｇ以上のシリカと水溶
性高分子バインダーを含む塗工層を設けることによって
一層鮮明なかつインク色再現性に優れた記録が得られる
ことを提案した。Among these, as a measure for recording resolution, density, and vividness of color tone, Japanese Patent Application Laid-Open No. 55-51583. 56-1
48583 and 56-148585, etc., it has been proposed to coat a support with a paint consisting of a silica pigment and a water-soluble polymer binder of 108/rn' or more. Particle size distribution (Rosin-Rammle
Further clarity and ink color reproducibility can be achieved by providing a coating layer containing silica and a water-soluble polymer binder with an even number of r distribution) of 10 or more and a specific surface area of 200 tn'/g or more by the BET method. It was suggested that an excellent record could be obtained.
更にインクジェット記録画像を耐水化するための方法と
しては特開昭５６−８４９９２．特開昭５９−２０６９
６特開昭５９−１４８８８９ 、特開昭６０−４９９９
０などに各種のカチオン性ポリマーをその表面に含有す
る記録媒体に水性インクを印写する方法が提案されてい
る。Furthermore, a method for making inkjet recorded images waterproof is disclosed in Japanese Patent Application Laid-Open No. 56-84992. Japanese Patent Publication No. 59-2069
6 JP-A-59-148889, JP-A-60-4999
A method has been proposed in which water-based ink is printed on a recording medium containing various cationic polymers, such as 0, on its surface.
この方法による耐水化は、インク中の直接染料や酸性染
料とこれらカチオン性ポリマーとの結合により、水に不
溶性のコンプレックスができることによるものである。Water resistance achieved by this method is due to the formation of a water-insoluble complex through the combination of direct dyes and acid dyes in the ink with these cationic polymers.
しかし、これらのカチオン性ポリマー等を使用した記録
紙にインクジェットカラー記録を施した場合、未添加の
記録紙と比較して画像耐水性の大幅な向上は認められる
が、なお、次のような欠点がみられる。However, when inkjet color recording is performed on recording paper using these cationic polymers, etc., the water resistance of the image is significantly improved compared to recording paper without additives, but there are still the following drawbacks: can be seen.
カラーインクジェット記録においては一般的にブラック
、シアン、マゼンタ、イエローの４基本色のインクを用
い、他色は各基本インクを重ね合せる減法混色によって
他色を表現している。普及型のカラーインクジェットプ
リンタは多くはシリアル方式のものであって、カラー混
色を得る場合、往と復で基本色の重ね順が逆になる。カ
チオン性ボ′リマーを耐水化剤としたものは、この混色
においてインクの重ね順によってその色合が違って見え
る、いわゆる色ズレが著しく大きくなる。In color inkjet recording, inks of four basic colors, black, cyan, magenta, and yellow, are generally used, and other colors are expressed by subtractive color mixing in which the basic inks are superimposed. Most popular color inkjet printers are serial type printers, and when obtaining mixed colors, the order of overlapping the basic colors is reversed in the forward and backward directions. When a cationic polymer is used as a water resistance agent, the so-called color shift, in which the color tone appears different depending on the order in which the inks are stacked in this color mixture, becomes extremely large.
その結果、例えば紫色の全面記録を往路シアン。As a result, for example, a full-scale record of purple is recorded in cyan.
マゼンタの順で記録し、復路はこの逆で記録をすること
の繰返しで得た場合、得られた画面は往路と復路で色ズ
レの為に縞模様として視認される欠点があった。又、例
えば黒色から赤へのように異なる色相の境界に於て、一
方から他方へあるいは互に色かにじみ込み境界線がはっ
きりしなくなる（にじみ込みと称す）という欠点もあっ
た。本発明者等は、特開昭６１−８９０８２号公報にお
いて、混色の重ね順の違いによる色ズレ及び画像解像度
の改善を目的としてシリコーンエマルジョンまたは水溶
性シリコーン化合物を含む塗料を塗布又は含浸してなる
インクジェット記録用シートのｔ是案を行った。しかし
ながらこの方法ではそのはっ水性のために顔料とバイン
ダーとの接着を妨げやすく塗工面の表面強度を低下させ
るという欠点があった。When the image is obtained by repeating recording in magenta order and in the reverse direction on the return trip, the resulting screen has the drawback that it is visually recognized as a striped pattern due to color misalignment on the outward and return trips. Another disadvantage is that at the boundary between different hues, such as from black to red, the colors bleed from one to the other or into each other, making the boundary line unclear (referred to as bleed). In JP-A No. 61-89082, the inventors of the present invention have disclosed that a paint containing a silicone emulsion or a water-soluble silicone compound is coated or impregnated for the purpose of improving color shift and image resolution due to differences in the order of layering of mixed colors. We made several plans for an inkjet recording sheet. However, this method has the disadvantage that its water repellency tends to hinder the adhesion between the pigment and the binder, resulting in a decrease in the surface strength of the coated surface.
本発明は、画像濃度や画像耐水性を保持し且つ塗工層の
表面強度を低下させることなくカラー記録における基本
色の重ね順に違いに起因する色ズレ即ち縞の改善、更に
は隣接する２色の境界線におけるインクの他色へのにじ
み込みを改善する事を目的としたインクジェット記録用
シートを）是イ共せんとするものである。The present invention aims to improve color misregistration, that is, stripes caused by differences in the overlapping order of basic colors in color recording, and to improve the color misalignment or stripes caused by differences in the overlapping order of basic colors in color recording, while maintaining image density and image water resistance, and without reducing the surface strength of the coating layer. We would like to share an inkjet recording sheet with the purpose of improving the bleeding of ink into other colors at the boundary line of the inkjet recording sheet.
本発明は、前述の問題点を解決すべく鋭意研究を重ねた
結果、水溶性染料を含有した水性インクを用いて記録像
を形成するインクジェット記録用シートにおいて、該シ
ートがカチオン性ポリマー及びカチオン界面活性剤を支
持体に塗布又は含浸させてなるものとすることによって
前述の目的を達成した本発明を達成した、
以下本発明につき詳述する。As a result of intensive research to solve the above-mentioned problems, the present invention provides an inkjet recording sheet in which a recorded image is formed using a water-based ink containing a water-soluble dye, in which the sheet has a cationic polymer and a cationic interface. The present invention has achieved the above-mentioned objects by coating or impregnating a support with an activator.The present invention will be described in detail below.
本発明のカチオン性ポリマーとしては、３級アミンある
いは／及び４級アンモニウム塩を含む重合物あるいは共
重合物であり、ポリアリルアミン、ジシアンジミドホル
マリン縮金物、ポリエチレンイミン、ポリエチレンイミ
ン４級アンモニウム塩化合物、ジメチルジアリルアンモ
ニウム塩重合物、（メタ）アクリル酸アルキルアンモニ
ウム塩瓜合物、（メタ）アクリルアミドアルキルアンモ
ニウム塩型合物、４級アンモニウム塩を含むアイオネン
等をあげることができる。The cationic polymer of the present invention is a polymer or copolymer containing a tertiary amine or/and a quaternary ammonium salt, such as polyallylamine, dicyandimide formalin condensate, polyethyleneimine, or polyethyleneimine quaternary ammonium salt. Examples include dimethyldiallylammonium salt polymers, (meth)acrylic acid alkylammonium salt polymers, (meth)acrylamidoalkylammonium salt type compounds, and ionene containing quaternary ammonium salts.
本発明のカチオン界面活性剤としては、アルキルアミン
類、エタノールアミン類及びポリオキシエチレン付加ア
ミン等の１級〜３級アミン塩酸塩や酢酸塩、更にこれら
の４級アンモニウム塩、エチレンジアミン、ジエチレン
ジトリアミン等のポリエチレンポリアミン類、その他Ｎ
、Ｎジエチレンジアミン、アミノエチルエタノールアミ
ン、ビワジン、グアニジン、ヒドラジン等のアミン類な
どが挙げられる。これらの中で耐水性も含めて効果の優
れたものとしては、アルキルアミンやオキシエチレン付
加アミンの４級アンモニウム塩をあげることができる。The cationic surfactants of the present invention include primary to tertiary amine hydrochlorides and acetates such as alkylamines, ethanolamines, and polyoxyethylene-added amines, as well as quaternary ammonium salts thereof, ethylenediamine, diethyleneditriamine, etc. polyethylene polyamines such as, other N
, N-diethylenediamine, aminoethylethanolamine, biwazine, guanidine, hydrazine, and other amines. Among these, quaternary ammonium salts of alkyl amines and oxyethylene-added amines can be mentioned as those having excellent effects including water resistance.
これらのカチオン性ポリマー及びカチオン界面活性剤を
用い“Ｃ記録シートを製造する一般的且つ好ましい方法
は、水溶性高分子バインダーと顔料とカチオン性ポリマ
ーと必要に応じて各種の添加剤を加えた混合スラリーに
、カチオン界面活性剤を添加した塗液を紙の表面に塗工
する方法である。A general and preferred method for producing a "C recording sheet" using these cationic polymers and cationic surfactants is to mix a water-soluble polymer binder, a pigment, a cationic polymer, and various additives as necessary. This is a method in which a coating liquid containing a cationic surfactant added to a slurry is applied to the surface of paper.
然し、この方法に限定されるものではなく、記録シート
に要求される品質等に応じて、カチオン性ポリマーとカ
チオン界面活性剤を併存させるいかなる方ン去も可ｒ七
である。However, the method is not limited to this method, and any method in which a cationic polymer and a cationic surfactant are used together may be used depending on the quality required for the recording sheet.
例えば、支持体上にバインダーとカチオン性ポリマーか
らなる第一層を塗布し、更にその上にバインダーととも
にあるいは単独でカチオン界面活性剤溶液を第２層とし
て塗布した積層構造のもの、あるいはカチオン何ミボリ
マーとカチオン界面活性剤を所要の添加剤とともに支持
体に含浸させる等である。含浸の方法どし、ではバルブ
スラリーにこれらを添加して抄込む方法、無サイズ原紙
にサイズプレスで浸透させる方法及び、これらの溶液中
に支持体を浸漬する方法等である。For example, a layered structure in which a first layer consisting of a binder and a cationic polymer is coated on a support, and then a cationic surfactant solution is coated as a second layer with or without a binder, or a cationic polymer For example, the support is impregnated with a cationic surfactant and necessary additives. The impregnation methods include adding these to bulb slurry and making paper, impregnating sizeless base paper with a size press, and immersing the support in these solutions.
顔料どしては、シリカ、合成珪酸塩、タルク。Pigments include silica, synthetic silicates, and talc.
カオリン、クレー、重質又は＠貿炭酸カルシウム、その
他の炭酸塩、酸性白土、水酸化アルミニウム、ケイソウ
土、酸化チタン、酸化亜鉛、硫酸バリウム、尿素ホルマ
リン樹脂粉末、エチレン樹脂微粉末、スチレン樹脂微粉
末等であり、これらを混合して使用することもできる。Kaolin, clay, heavy or @trade calcium carbonate, other carbonates, acid clay, aluminum hydroxide, diatomaceous earth, titanium oxide, zinc oxide, barium sulfate, urea formalin resin powder, ethylene resin fine powder, styrene resin fine powder etc., and a mixture of these can also be used.
水溶性高分子バインダーとしては、ＰＶＡ、酸化でんろ
−ん、エーテル化でんぷん、その他のでんぷん話導体、
ゼラチン、カゼイン、カルボキシメチルセルロース５ヒ
ドロキシエチルセルロース。Examples of water-soluble polymer binders include PVA, oxidized starch, etherified starch, other starch conductors,
Gelatin, casein, carboxymethylcellulose 5-hydroxyethylcellulose.
その他のセルロース話導体１ポリビニルピロリドン等を
単独あるいは併用して使用する。更に接着剤としては、
スチレン・ブタジェン共重合物、メチルメタクリレート
・ブタジェン共重合物、アクリル酸エステル共重合物、
ポリ酢酸ビニル、エチレン・酢酸ビニル共重合などのラ
テックス、エマルジョンも使用可能である。Other cellulose conductors 1 Polyvinylpyrrolidone and the like are used alone or in combination. Furthermore, as an adhesive,
Styrene/butadiene copolymer, methyl methacrylate/butadiene copolymer, acrylic ester copolymer,
Latexes and emulsions such as polyvinyl acetate and ethylene/vinyl acetate copolymer can also be used.
上記のうち顔料としてはシリカ系のものが良く、なかで
も二酸化珪素を主成分とする湿式法による無定形シリカ
が好適であり、これに水溶性高分子バインダーとしてＰ
ＶＡ （ポリビニルアルコール）を組合わせたもの・が
画像の濃度、鮮明性の点で特に好ましいものである。Among the above pigments, silica-based pigments are preferred, and among them, wet-processed amorphous silica containing silicon dioxide as the main component is preferred, and Pigment is used as a water-soluble polymer binder.
A combination of VA (polyvinyl alcohol) is particularly preferred in terms of image density and sharpness.
このほか添加剤として、顔料分散剤、界面活性剤、消泡
剤２着色剤、酸化防止剤、紫外線吸収剤、ｍ型剤、粘度
調節剤、バインダーの架橋耐水化剤等が必要に応じて適
宜カチオン性ポリマーやカチオン界面活性剤とともに使
用できる。In addition, as additives, pigment dispersants, surfactants, antifoaming agents, colorants, antioxidants, ultraviolet absorbers, M-type agents, viscosity modifiers, binder crosslinking waterproofing agents, etc. may be added as appropriate. Can be used with cationic polymers and cationic surfactants.
これらの添加剤のうち、ノニオン界面活性剤や両性界面
活性剤は、画像の鮮明度および、にじみ等の点が一層改
善される点で好ましいものである。Among these additives, nonionic surfactants and amphoteric surfactants are preferable because they further improve image clarity and blurring.
効果の優れたノニオン界面活性剤の例としては、ポリオ
キシエチレン話導体として、ポリオキシエチレン−オキ
シプロピレン共重合物、ポリオキシエチレンラウリルエ
ーテル、ポリオキシエチレンモノラウレート、ポリオキ
シエチレンノニルフェニルエーテル、ポリオキシエチレ
ンオレイルエーテル、ポリオキシエチレン千ノオレエー
ト。Examples of highly effective nonionic surfactants include polyoxyethylene conductors such as polyoxyethylene-oxypropylene copolymer, polyoxyethylene lauryl ether, polyoxyethylene monolaurate, polyoxyethylene nonylphenyl ether, Polyoxyethylene oleyl ether, polyoxyethylene oleyl ether.
ポリオキシエチレン高級アルコールエーテル、ポリオキ
シエチレンソルビタントリオレエート等があり、更にソ
ルビタンモノラウレート、ポリエチレングリコールジス
テアレート、グリセロールモノステアレート、フッ素系
ノニオン界面活性剤、シリコン系界面活性剤等を挙げる
ことができる。There are polyoxyethylene higher alcohol ethers, polyoxyethylene sorbitan trioleate, etc., and further examples include sorbitan monolaurate, polyethylene glycol distearate, glycerol monostearate, fluorine-based nonionic surfactants, silicone-based surfactants, etc. I can do it.
両界面活性剤の例としては、ジメチルアルキル（ヤシ）
ベタイン、ジメチルアルキルラウリルベタイン、ジメチ
ルアルキルステアリルベタイン。Examples of both surfactants include dimethylalkyl (coconut)
Betaine, dimethylalkyllaurylbetaine, dimethylalkylstearylbetaine.
２−アルキル−Ｎ−カルボキシエチル−Ｎ−ヒドロキシ
エチルイミダゾリニウムベタイン、２−アルキル−Ｎ−
カルボキシメチル−Ｎ−ヒドロキシエチルイミダゾリニ
ウムベタイン等が挙げられる。2-Alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine, 2-alkyl-N-
Examples include carboxymethyl-N-hydroxyethylimidazolinium betaine.
本発明のカチオン性ポリマーの塗布量又は含浸量は、固
形分として０．０５〜２．５ ｇ／ｒｒｌ程度、好まし
くはｏ、ｉ〜１．５ ｇ／ｍ”で十分な画像耐水効果が
発現される。又のカチオン赤面活性剤の塗布量又は含浸
量は固形分として０．０１〜２．５ ｇｌｒｄ程度、好
ましくは０．０５〜１．５ ｇ／ｒｎ”で本発明の目的
を十分に達成することができる。更に加えてもよいノニ
オン界面活性剤あるいは両性界面活性剤の塗布量又は含
浸量は固形分として０．０１〜２．５ ｇ／ｄの範囲で
ある。これらの塗料の塗布方法としては従来法をそのま
ま用いることが可能である。即ち、サイズプレス、ゲー
トクルコーター。エアナイフコーター、ブレードコータ
ー、スプレー等が利用でき、カチオン性ポリマー及びカ
チオン界面活性剤の単独もしくは混合液全体の塗布は、
塗布量が多ければオフマシン塗工で行い、少なければオ
ンマシン塗工が可能である。The amount of coating or impregnation of the cationic polymer of the present invention is approximately 0.05 to 2.5 g/rrl in terms of solid content, preferably 1 to 1.5 g/m'' to achieve a sufficient image water resistance effect. The amount of coating or impregnation of the cationic blush activator is approximately 0.01 to 2.5 glrd as solid content, preferably 0.05 to 1.5 g/rn'', which is sufficient for the purpose of the present invention. can be achieved. The amount of coating or impregnation of a nonionic surfactant or amphoteric surfactant that may be added is in the range of 0.01 to 2.5 g/d as solid content. Conventional methods can be used as they are for applying these paints. Namely, size press, gate coater. Air knife coaters, blade coaters, sprays, etc. can be used to apply the cationic polymer and cationic surfactant alone or as a mixture.
If the amount to be applied is large, off-machine coating is possible, and if it is small, on-machine coating is possible.
カチオン性ポリマーとカチオン界面活性剤の併用が、色
ズレ、記録編及びにじみ込みを改善する理由は明らかで
はないが、次のように推定される。Although it is not clear why the combined use of a cationic polymer and a cationic surfactant improves color shift, recording, and bleeding, it is presumed as follows.
記録層にカチオン性ポリマーを含有させた記録紙を往復
方式のプリンタで混色印字した場合、先に吐出されたイ
ンク粒子中の染料は表層に近いカチオン性ポリマーに強
く吸着捕獲されドツトの広がりも′小さい、この上に２
色目のインク粒子が到達した場合、表層のカチオン性ポ
リマーの吸着座席は先のインク中の染料に大部分占有さ
れて、２色目のインク中の染料の吸着座席が少ないこと
や、先のインク中の染料が強く捕獲されている等の理由
から、両者のインクの混合−不十分となり、２色目のイ
ンク色が上包として強く出ること、及び先行するインク
の広がりを越えて２色目のインクが広がることによって
大きな色ズレ、記９１ ＫＡが生ずるものと考えられる
。又カチオン性ポリマーの存在はインクの支持体内部へ
の浸透を遅くうせる結果、横方向への移動が多くなって
、にじみ込みが発生し易すくなるものと考えられる。When mixed-color printing is performed using a reciprocating printer on recording paper whose recording layer contains a cationic polymer, the dye in the ink particles ejected first is strongly adsorbed and captured by the cationic polymer near the surface layer, causing the dots to spread. Small, 2 on this
When ink particles of a different color arrive, most of the adsorption seats of the cationic polymer on the surface layer are occupied by the dye in the previous ink, and there are fewer adsorption seats for the dye in the second color ink, or Due to reasons such as the dye being strongly captured, the mixing of both inks becomes insufficient, and the second color ink appears strongly as an overlay, and the second color ink exceeds the spread of the preceding ink. It is thought that the widening causes a large color shift, ie, 91 KA. It is also believed that the presence of the cationic polymer slows down the penetration of the ink into the support, resulting in increased movement in the lateral direction, making bleeding more likely.
これに対し本発明のようにカチオン性ポリマーとカチオ
ン赤面活性剤を併用するならば、カチオン界面活性剤は
カチオン性ポリマーより表層に存在するためか、先行す
るインク染料の多くは優先的にカチオン界面活性剤と反
応する。この反応で生ずるコンプレックスは、カチオン
性ポリマーとのコンプレックスより著しく弱い結合であ
り、しかも同時に存在するカチオン界面活性剤ミセルに
よるコンプレックスの強い可溶化作用によって、２色目
のインクと先行したインクの混合が円滑に行われるとと
もに定着すると推定される。これによって色ズレ、記録
編のないカラー画像が得られる。またにじみ込みは、カ
チオン界面活性剤の存在によって、インクの支持体中へ
の浸透が促進されて改善されるものと為えられる。これ
らのカチオン赤面活性剤の作用番Ｊカチオン性ポリマー
の存在下で顕著であるが、その理由は不明である。更に
画像耐水性については、簡単なぬれに対してカチオン界
面活性剤でも多少効果はあるが、水中への侵せきなどの
厳しい条件下では、界面活性剤が染料としても溶出して
いく過程でインク染料のカチオン性ポリマーへの再定着
によって耐水性が確保されることになる。On the other hand, if a cationic polymer and a cationic blush active agent are used together as in the present invention, most of the preceding ink dyes are preferentially absorbed by the cationic surface, perhaps because the cationic surfactant is present in the surface layer rather than the cationic polymer. Reacts with activators. The complex generated by this reaction has a significantly weaker bond than the complex with the cationic polymer, and the strong solubilization effect of the complex due to the cationic surfactant micelles present at the same time facilitates the mixing of the second color ink and the preceding ink. It is estimated that it will become established as soon as it is implemented. As a result, a color image without color shift or recording stitches can be obtained. In addition, it is considered that the presence of the cationic surfactant promotes the penetration of the ink into the support, thereby improving the bleeding. The effect of these cationic blush active agents is significant in the presence of cationic polymers, but the reason for this is unclear. Furthermore, regarding image water resistance, cationic surfactants are somewhat effective for simple wetting, but under severe conditions such as immersion into water, the surfactant dissolves as a dye, causing the ink to deteriorate. Water resistance will be ensured by refixing the dye to the cationic polymer.
以下実施例により説明する。尚、実施例中の部及び％は
特にことわらないかぎり重量部及び重量％を表す。This will be explained below using examples. Incidentally, parts and % in the examples represent parts by weight and % by weight unless otherwise specified.
又、得られた記録紙の品質テスト法は次の通りである。The method for testing the quality of the obtained recording paper is as follows.
（１）記録濃度：インクジェットカラープリンタ（シャ
ープ■製； １Ｏ−７００）を使用してブラック。(1) Recording density: Black using an inkjet color printer (manufactured by Sharp ■; 1O-700).
シアン１．マゼンタ、イエローの４色の全面記録を行い
、ブラック部分についてブラック用ビジュアル、シアン
部分についてはシアン用レッド、マゼンタ部分について
はマゼンタ用グリーン、イエロ一部分についてはイエロ
ー用ブルーの各ＳＰＩフィルターを用いて反射４度肝（
マクベス社製：ＲＤ９１５）により測定した反射光学濃
度の合計値で示した。Cyan 1. The entire surface is recorded in four colors, magenta and yellow, and the black part is reflected using the visual for black, the cyan part is reflected using the red for cyan, the magenta part is reflected using the green for magenta, and the yellow part is reflected using the blue for yellow. 4th degree liver disease (
It is shown as the total value of reflective optical density measured by Macbeth Co., Ltd.: RD915).
（２）画像耐水性二上記にて記録測定したサンプルを２
４時間市水に浸漬した後、記録物を取出し乾燥させ、再
度記録濃度を測定しその記録濃度変化率（零）で表した
。(2) Image water resistance 2 The sample recorded and measured above was
After being immersed in city water for 4 hours, the recorded material was taken out and dried, and the recorded density was measured again and expressed as a rate of change in recorded density (zero).
（３）色ズレ及び記録編：紫（シアン−マゼンタ）、赤
（マゼンタ−イエロー）、及び緑（イエロー−シアン）
の３混色について測定した。(3) Color shift and recording: Purple (cyan-magenta), red (magenta-yellow), and green (yellow-cyan)
Measurements were made for three color mixtures.
上記３色を往復印字にてそれぞれ全面記録を行りた後、
サクラマイクロデンシトメータＰＤＭ５（小西六写真工
業■製）により、往路部分復路部分についてそれぞれ重
ね色の色濃度を測定する。例えば緑の場合はシアン、イ
エローの２色の記録濃度を測定し、シアン成分の往路と
復路の濃度差Δ１とイエロー成分の往路と復路の濃度差
Δ２とを加えてΔ、＋Δ、＝ｄを緑の色ズレの度合とし
た。他の混色の色ズレについても同様に求めた。色ズレ
の評価は３混色の色ズレの大きさｄの合計で行った。After recording the above three colors on the entire surface by reciprocating printing,
Using Sakura Microdensitometer PDM5 (manufactured by Konishiroku Photo Industry ■), the color density of the overlapping colors was measured for each of the outgoing and returning portions. For example, in the case of green, measure the recording densities of two colors, cyan and yellow, and add the density difference Δ1 of the cyan component between the outward and return passes and the density difference Δ2 of the yellow component between the outward and return passes to obtain Δ, +Δ, = d. It was defined as the degree of green color shift. The color deviations of other mixed colors were similarly determined. The color shift was evaluated based on the total color shift size d of the three mixed colors.
記録線は色ズレの大きさで表わされる。The recording line is expressed by the size of the color shift.
（４）にじみ込み：インクの付着量が異なる単色−混色
の境界線において顕著であり、特に目立ち易い、ブラッ
ク／赤、シアン／赤、マゼンタ／縁、イエロー／紫の４
つの組合せについてそれぞれ相隣りあう様なパターンを
つくり、境界線上のにじみ込み巾を目視にて判定した。(4) Bleeding: It is noticeable at the boundary line between a single color and a mixed color, where the amount of ink adhered to differs, and is particularly noticeable in the four colors of black/red, cyan/red, magenta/edge, and yellow/purple.
Adjacent patterns were created for each of the two combinations, and the width of the bleeding on the boundary line was visually determined.
にじみ込みなし−・−Ａ 、 ０．３ ｍｍ以下・・・
Ｂ 、 ０．３ ｍｍ〜１ ｍｍ・・・Ｃ、１ｎｏｎ以
上・・・Ｄとした。Ａ及びＢは実用範囲である。No bleeding--A, 0.3 mm or less...
B, 0.3 mm to 1 mm...C, 1non or more...D. A and B are within the practical range.
（５）記録面の表面強度：
市販のセロハンテープにチバン１８ｍｍ巾）を用いて、
各サンプルの記録面に長さ約７ｃｍ程一定の抑圧で貼付
した後、１分後に片端からセロハンテープを剥離した際
、塗工層のセロテープ側への剥離状態をみる。(5) Surface strength of recording surface: Using commercially available cellophane tape with a width of 18 mm,
After pasting a length of about 7 cm on the recording surface of each sample with constant pressure, the cellophane tape was peeled off from one end after 1 minute, and the state of peeling of the coating layer toward the cellophane tape side was observed.
Ａ：擾 ：塗工層の剥離は極めて少ない。A: 澾 : Peeling of the coating layer is extremely small.
Ｂ：良 ：塗工層の剥離が若干みられる。B: Good: Slight peeling of the coating layer is observed.
Ｃ：不可：塗工層の剥離が多い。C: Not acceptable: There was a lot of peeling of the coating layer.
［実施例１コ
顔料として合成シリカ（日本シリカニ業■製：ニップシ
ールＥ２２０Ａ）１７％スラリー１０００部に、バイン
ダーとして完全ケン化ポリビニールアルコール（クラレ
■製、ＰＶＡ１１７）の１０％水溶液３００部を混合し
水を加えて固形分濃度１５％の塗料を調製し、更にこの
塗料１０００部にたいして、カチオン性ポリマーとして
ポリジメチルジアリルアンモニウムクロライド（日東紡
■製；ＰＡＳＨ−１ＯＬ）の２８％水溶液２７部を添加
しくａ）液とした。この（ａ） ’ｄｔに更に（ｂＪ液
として、ドデシルトリメチルアンモニウムクロライド（
日本油脂■製；カチオンＢＢ）の５０％液３部を加えて
塗布液とした。支持体は、フリーネス３５０ｍ１ＬのＬ
ＢＫＰ８０部およびフリーネス４００ ｍ℃のＮＢＫ
Ｐ２０部から成る原料バルブに、軽質炭酸カルシウム粉
体（白石工業０菊製、ＰＣ）を２０部添加し、長網マシ
ンで抄造した秤量６０ ｇ／ｍ”の中性サイズ紙を用い
た、この支持体上に前記の各混合塗料を塗布量が約１０
ｇ／ｍ”になるようにワイヤーバーで塗布した。更にこ
れらの紙のベック平滑度が９０〜１４０秒になるように
テストカレンダー（自利ロール■製）にしてインクジェ
ット記録用シートを得た。[Example 1] 1000 parts of a 17% slurry of synthetic silica (Nip Seal E220A, manufactured by Nippon Shirikani Industry ■) as a pigment was mixed with 300 parts of a 10% aqueous solution of fully saponified polyvinyl alcohol (manufactured by Kuraray ■, PVA117) as a binder. Add water to prepare a paint with a solid content concentration of 15%, and further add 27 parts of a 28% aqueous solution of polydimethyldiallylammonium chloride (manufactured by Nittobo Corporation; PASH-1OL) as a cationic polymer to 1000 parts of this paint. a) It was made into a liquid. In addition to this (a) 'dt (bJ liquid, dodecyltrimethylammonium chloride (
Three parts of a 50% solution of Cation BB) manufactured by NOF ■ was added to prepare a coating solution. The support is L with freeness 350ml 1L.
NBK with 80 parts BKP and freeness 400 m℃
20 parts of light calcium carbonate powder (manufactured by Shiraishi Kogyo Kiku, PC) was added to a raw material valve consisting of 20 parts of P, and a neutral size paper with a basis weight of 60 g/m" was made using a fourdrinier machine. The coating amount of each of the above mixed paints on the support is about 10
g/m" using a wire bar. Furthermore, these papers were subjected to a test calender (manufactured by Jiri Roll ■) to obtain inkjet recording sheets such that the Bekk smoothness of these papers was 90 to 140 seconds.
［比較例１〜４コ
実施例１において、（ａ） ？ａ中のカチオン性ポリマ
ー：ポリジメチルジアリルアンモニウム塩を添加しない
以外は同様にして記録用シートを得た（比較例１）、ま
た実施例１において、（ｂＪ液を添加しない以外は同様
にして記録用シートを得た（比較例２）。更に実施例１
の（ａ） ？ＦＬのポリジメチルジアリルアンモニウム
塩にかえてポリアリルアミジ塩酸塩（日東紡■製、ＰＡ
＾−）ＩＣ１ＬＨ） ３０％水溶液２５部を加え、か
つ（ｂｌ液を添加しない以外は同様にして記録用シート
を得た（比較例３）、更に実施例１の（ｂ）液のカチオ
ン界面活性剤にかえてポリオキシエチレントリデシルエ
ーテル（日本油脂■製；ノニオンＴ２Ｏ８，５）を１０
０％液として１．５部加えた以外は同様にして記録用シ
ートを得たｌ（比較例４）。[Comparative Examples 1 to 4 In Example 1, (a)? Cationic polymer in a: A recording sheet was obtained in the same manner except that polydimethyldiallylammonium salt was not added (Comparative Example 1). (Comparative Example 2).Furthermore, Example 1
(a) ? Polyallylamidihydrochloride (manufactured by Nittobo, PA) was used instead of polydimethyldiallylammonium salt of FL.
A recording sheet was obtained in the same manner except that 25 parts of a 30% aqueous solution was added (Comparative Example 3), and 25 parts of a 30% aqueous solution was added (Comparative Example 3). Polyoxyethylene tridecyl ether (manufactured by NOF ■; nonionic T2O8,5) was added to
A recording sheet was obtained in the same manner except that 1.5 parts of 0% liquid was added (Comparative Example 4).
［実施例２］
実施例１の（ａ）液にノニオン界面活性剤としてポリオ
キシエヂレニノノニルフエニルエーテル（ミヨシ油脂調
＞製；ベレテックス１２２３）を１００％液として１．
５部加えた以外は実施例１と同様にして記録用シートを
得た。[Example 2] 1. Polyoxyethylene nononyl phenyl ether (manufactured by Miyoshi Yushi Choi Co., Ltd.; Beletex 1223) was added as a nonionic surfactant to the solution (a) of Example 1 as a 100% solution.
A recording sheet was obtained in the same manner as in Example 1 except that 5 parts were added.
［実施例３］
実施例１において、（ａ）液のポリジメチルジアリルア
ンモニウム塩にかえてポリアリルアミン塩酸塩（同上）
３０％水溶？ｖ、２５部を加えた以外は同様にして記録
用シートを得た。[Example 3] In Example 1, polyallylamine hydrochloride (same as above) was used instead of polydimethyldiallylammonium salt in solution (a).
30% water soluble? A recording sheet was obtained in the same manner except that 25 parts of V.
Ｕ実施例４コ
実施例１の（ｂ）液のドデシルトリメチルアンモニウム
クロライドに代えてポリオキシエチレンアルギル第４級
アンモニウム塩（ライオンアクゾ■製、エソカード０／
１２） ７５％２部を加えた以外は実施１列１と同様
にして記録用シートを得た。U Example 4 Polyoxyethylene argyl quaternary ammonium salt (manufactured by Lion Akzo ■, Eso Card 0/
12) A recording sheet was obtained in the same manner as in Example 1, Row 1, except that 2 parts of 75% was added.
［実施例５コ
実施例Ｉにおいて、（ａ）液に両性界面活性剤としてジ
メチルアルキルラウリルヘタイン（花王石齢■製、アン
ヒトール２０ＢＳ）を１００％ｖ夜として１．５部加え
た以外は同様にして記録用シートを得た。[Example 5] Same as Example I except that 1.5 parts of dimethylalkyl laurylhetaine (manufactured by Kao Shirei, Amhitol 20BS) as an amphoteric surfactant was added to the solution (a) as 100% v. A recording sheet was obtained.
〔実施例６〕
カチオン性ポリマーとして、β−メタクロイルオキシエ
チルトリメチルアンモニウムクロライド重合物の２０％
水溶液５０部と、実施例１で使用したカチオン界面活性
剤としてドデシルトリメチルアンモニウムクロライド（
カチオンＢＢ）の５０％液６部をバインダー水溶液であ
るポリビニルアルコール（クラレ■製；ＰνＡ １１７
）の１０％水溶７Ｉ！３００部に混合した塗液を、実
施例１で使用した中性原紙にサイズプレスで両面より１
５ｇ／ｒｎ’となるように塗布含浸させ、ベック平滑度
約６０秒となるよう力１ノンダ掛けして、インクジェッ
ト記録用シー１−を得た。[Example 6] As a cationic polymer, 20% of β-methacroyloxyethyltrimethylammonium chloride polymer
50 parts of an aqueous solution and dodecyltrimethylammonium chloride (as the cationic surfactant used in Example 1)
Add 6 parts of a 50% solution of cation BB) to polyvinyl alcohol (manufactured by Kuraray ■; PνA 117), which is an aqueous binder solution.
) 10% water-soluble 7I! Apply 300 parts of the mixed coating liquid to the neutral base paper used in Example 1 from both sides using a size press.
The film was coated and impregnated at a concentration of 5 g/rn', and a force of 1 was applied to obtain a Bekk smoothness of approximately 60 seconds to obtain an inkjet recording sheet 1-.
［比較例５］
実施例６において、カチオン界面活性剤を添加しなかっ
たほかは実施例６と同様にして記録シートを得た。[Comparative Example 5] A recording sheet was obtained in the same manner as in Example 6 except that the cationic surfactant was not added.
［比較例６コ
実施例７において、カチオン界面活性剤の積層塗布を行
なわなかったほかは実施例７と同様にして記録シートを
得た。[Comparative Example 6] A recording sheet was obtained in the same manner as in Example 7, except that the cationic surfactant was not applied in layers.
［比較例７］
カチオン性ポリマーとしてβ−メタクロイルオキシメチ
ルトリメチルアンモニウムクロライドとスチレンの共重
合体５％水溶液４００ｇを酸化デンプンの１０水溶液８
００部によく混和した塗液を実施例１と同じ支持体上に
１０ｇ／ｒｎ’塗布、乾燥した。ついでこの塗布層上に
カチオン界面活性剤としてラフリルトリメチルアンモニ
ウムクロライド（花王石鹸■製コータミン２４Ｐ）を０
．８ ｇ／ｒｒｌ積層塗布し乾燥して記録シートを得た
。[Comparative Example 7] 400 g of a 5% aqueous solution of a copolymer of β-methacroyloxymethyltrimethylammonium chloride and styrene as a cationic polymer was added to a 10 aqueous solution of oxidized starch.
00 parts of the coating solution was coated on the same support as in Example 1 at 10 g/rn' and dried. Next, 0% of lafuryltrimethylammonium chloride (Cortamine 24P manufactured by Kao Soap) was applied as a cationic surfactant on this coating layer.
．． A recording sheet was obtained by applying a layered coating of 8 g/rrl and drying.
実施例１〜７及び比較例１〜６で作成した各記録シート
を先に述べた方法で試験し、その結果を色ズレ（縞）、
にじみ込み及び表面強度について表−１に示し、基本性
能である発色濃度と耐水性について表−２に示した。Each of the recording sheets prepared in Examples 1 to 7 and Comparative Examples 1 to 6 was tested by the method described above, and the results were evaluated for color misregistration (stripes),
Table 1 shows the bleeding and surface strength, and Table 2 shows the basic performance, color density and water resistance.
〔発明の効果）
上述したように、カチオン性ポリマーとカチオン性界面
活性剤を支持体に塗布または含浸したインクジェット用
記録シートは、優れた発色濃度や耐水性を維持したまま
、カチオン性ポリマーを使用することによる欠点即ち、
インクの重ね順の違いによる色ズレ及びその結果として
生ずる縞模様や、異なる色の境界で発意する色のにじみ
込みを顕著に改善することができたので、原画像の再生
性に優れたインクジェット記録像を得ることができる。[Effects of the Invention] As described above, an inkjet recording sheet in which a support is coated or impregnated with a cationic polymer and a cationic surfactant uses the cationic polymer while maintaining excellent color density and water resistance. The disadvantages of
It was possible to significantly improve color misregistration caused by differences in the order of ink stacking, the resulting striped patterns, and color bleeding that occurs at boundaries between different colors, resulting in inkjet recording with excellent reproduction of original images. You can get the image.
Claims (3)
を形成するインクジェット記録用シートにおいて、該シ
ートが支持体にカチオン性ポリマー及びカチオン界面活
性剤を支持体に塗布または含浸してなることを特徴とす
るインクジェット記録用シート。(1) In an inkjet recording sheet that forms a recorded image using a water-based ink containing a water-soluble dye, the sheet is formed by coating or impregnating a cationic polymer and a cationic surfactant on the support. An inkjet recording sheet featuring:
は４級アンモニウム塩を含む重合物であることを特徴と
する特許請求の範囲第１項記載のインクジェット記録用
シート。(2) The inkjet recording sheet according to claim 1, wherein the cationic polymer is a polymer containing a tertiary amine and/or a quaternary ammonium salt.
キシエチレン付加アミンの各４級アンモニウム塩である
ことを特徴とする特許請求の範囲第１項又は第２項記載
のインクジェット記録用シート。(3) The inkjet recording sheet according to claim 1 or 2, wherein the cationic surfactant is a quaternary ammonium salt of an alkylamine or an oxyethylene-added amine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61311737A JP2514194B2 (en) | 1986-12-26 | 1986-12-26 | Inkjet recording sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61311737A JP2514194B2 (en) | 1986-12-26 | 1986-12-26 | Inkjet recording sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63162275A true JPS63162275A (en) | 1988-07-05 |
| JP2514194B2 JP2514194B2 (en) | 1996-07-10 |
Family
ID=18020865
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61311737A Expired - Lifetime JP2514194B2 (en) | 1986-12-26 | 1986-12-26 | Inkjet recording sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2514194B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0673781A1 (en) * | 1994-02-15 | 1995-09-27 | Xerox Corporation | Recording sheets containing amine salts and quaternary choline halides |
| JP2003527984A (en) * | 2000-03-20 | 2003-09-24 | エスアールアイ インターナショナル | Preparation of light-emitting, highly reflective and / or metal-like images on substrate surfaces |
| US6689432B2 (en) | 2000-01-28 | 2004-02-10 | Oji Paper Co., Ltd. | Ink jet recording material |
| JP2005188007A (en) * | 2003-12-26 | 2005-07-14 | Fuji Xerox Co Ltd | Recording paper and method for recording picture image using the same |
| US7060335B2 (en) * | 1999-12-27 | 2006-06-13 | Canon Kabushiki Kaisha | Recording medium, method of manufacturing the same and image forming method |
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| JPS55144172A (en) * | 1979-04-27 | 1980-11-10 | Fuji Photo Film Co Ltd | Ink jet recording method |
| JPS55150396A (en) * | 1979-05-14 | 1980-11-22 | Fuji Photo Film Co Ltd | Method for attaining waterproof property to ink jet recorded sheet |
| JPS5699693A (en) * | 1980-01-14 | 1981-08-11 | Ricoh Co Ltd | Ink jet recording method |
| JPS57191084A (en) * | 1981-05-22 | 1982-11-24 | Canon Inc | Recording medium for ink jet and recording method using thereof |
| JPS58147469A (en) * | 1982-02-25 | 1983-09-02 | Mitsubishi Paper Mills Ltd | Ink jet recording method |
| JPS58177390A (en) * | 1982-04-13 | 1983-10-18 | Mitsubishi Paper Mills Ltd | Recording sheet |
| JPS5943065A (en) * | 1982-09-03 | 1984-03-09 | Oji Yuka Gouseishi Kk | Coating material and thermoplastic resin film coated therewith |
| JPS5952689A (en) * | 1982-09-17 | 1984-03-27 | Mitsubishi Paper Mills Ltd | Recording paper |
| JPS6011389A (en) * | 1983-07-01 | 1985-01-21 | Mitsubishi Paper Mills Ltd | Ink jet recording paper |
| JPS6067190A (en) * | 1983-09-22 | 1985-04-17 | Ricoh Co Ltd | Ink jet recording medium |
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| JPS6174880A (en) * | 1984-09-21 | 1986-04-17 | Jujo Paper Co Ltd | Ink jet recording paper |
| JPS6195977A (en) * | 1984-10-18 | 1986-05-14 | Daio Seishi Kk | Ink jet recording paper |
| JPS61132376A (en) * | 1984-11-30 | 1986-06-19 | Lion Corp | Ink jet recording sheet |
| JPS61134291A (en) * | 1984-12-03 | 1986-06-21 | Kuraray Co Ltd | Ink jet recording paper |
| JPS61252189A (en) * | 1985-04-17 | 1986-11-10 | Mitsubishi Yuka Fine Chem Co Ltd | Ink jet recording paper |
| JPS62221592A (en) * | 1986-03-25 | 1987-09-29 | Japan Synthetic Rubber Co Ltd | Coating composition for ink jet recording paper |
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1986
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| JPS55144172A (en) * | 1979-04-27 | 1980-11-10 | Fuji Photo Film Co Ltd | Ink jet recording method |
| JPS55150396A (en) * | 1979-05-14 | 1980-11-22 | Fuji Photo Film Co Ltd | Method for attaining waterproof property to ink jet recorded sheet |
| JPS5699693A (en) * | 1980-01-14 | 1981-08-11 | Ricoh Co Ltd | Ink jet recording method |
| JPS57191084A (en) * | 1981-05-22 | 1982-11-24 | Canon Inc | Recording medium for ink jet and recording method using thereof |
| JPS58147469A (en) * | 1982-02-25 | 1983-09-02 | Mitsubishi Paper Mills Ltd | Ink jet recording method |
| JPS58177390A (en) * | 1982-04-13 | 1983-10-18 | Mitsubishi Paper Mills Ltd | Recording sheet |
| JPS5943065A (en) * | 1982-09-03 | 1984-03-09 | Oji Yuka Gouseishi Kk | Coating material and thermoplastic resin film coated therewith |
| JPS5952689A (en) * | 1982-09-17 | 1984-03-27 | Mitsubishi Paper Mills Ltd | Recording paper |
| JPS6011389A (en) * | 1983-07-01 | 1985-01-21 | Mitsubishi Paper Mills Ltd | Ink jet recording paper |
| JPS6067190A (en) * | 1983-09-22 | 1985-04-17 | Ricoh Co Ltd | Ink jet recording medium |
| JPS6172581A (en) * | 1984-09-17 | 1986-04-14 | Canon Inc | Ink jet recording system |
| JPS6174880A (en) * | 1984-09-21 | 1986-04-17 | Jujo Paper Co Ltd | Ink jet recording paper |
| JPS6195977A (en) * | 1984-10-18 | 1986-05-14 | Daio Seishi Kk | Ink jet recording paper |
| JPS61132376A (en) * | 1984-11-30 | 1986-06-19 | Lion Corp | Ink jet recording sheet |
| JPS61134291A (en) * | 1984-12-03 | 1986-06-21 | Kuraray Co Ltd | Ink jet recording paper |
| JPS61252189A (en) * | 1985-04-17 | 1986-11-10 | Mitsubishi Yuka Fine Chem Co Ltd | Ink jet recording paper |
| JPS62221592A (en) * | 1986-03-25 | 1987-09-29 | Japan Synthetic Rubber Co Ltd | Coating composition for ink jet recording paper |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0673781A1 (en) * | 1994-02-15 | 1995-09-27 | Xerox Corporation | Recording sheets containing amine salts and quaternary choline halides |
| US5759701A (en) * | 1994-02-15 | 1998-06-02 | Xerox Corporation | Recording sheets containing amine salts and quaternary choline halides |
| US7060335B2 (en) * | 1999-12-27 | 2006-06-13 | Canon Kabushiki Kaisha | Recording medium, method of manufacturing the same and image forming method |
| US6689432B2 (en) | 2000-01-28 | 2004-02-10 | Oji Paper Co., Ltd. | Ink jet recording material |
| JP2003527984A (en) * | 2000-03-20 | 2003-09-24 | エスアールアイ インターナショナル | Preparation of light-emitting, highly reflective and / or metal-like images on substrate surfaces |
| JP2005188007A (en) * | 2003-12-26 | 2005-07-14 | Fuji Xerox Co Ltd | Recording paper and method for recording picture image using the same |
| JP4604486B2 (en) * | 2003-12-26 | 2011-01-05 | 富士ゼロックス株式会社 | Recording paper and image recording method using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2514194B2 (en) | 1996-07-10 |
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