JPS6072785A - Ink jet recording paper - Google Patents

Abstract

PURPOSE:To obtain a high-performance ink jet recording paper having a sufficient water resistance and a persistent light resistance by contacting a direct dye and an acid dye with a specific polyethyleneimine quaternary ammonium compound on a recording paper. CONSTITUTION:On a base paper, a polyethyleneimine and a halogenated hydrocarbon or a protonic acid are reacted and then reacted with an alkylene oxide, or a polyethyleneimine, an alkylene oxide, and a halogenated hydrocarbon are reacted to obtain a polyethyleneimine quaternary ammonium compound. A coat layer containing the polyethyleneimine quaternary ammonium compound, an antioxidant, and/or an ultraviolet rays absorber is formed on the base paper. The amount of the coat layer is preferably in the range of 0.01-10g/m<2>, particularly 0.1-2g/m<2>.

Description

[Detailed description of the invention]

The present invention relates to recording paper for inkjet recording. More specifically, the present invention relates to an inkjet recording paper with improved water resistance and light resistance of printed records. -1- The inkjet recording method is widely used in facsimiles, various types of paper, etc. because it generates less noise, can perform high-speed recording, can print in multiple colors, and can use any paper such as plain paper, medium-quality paper, and plain paper. It is used in a wide range of fields such as recording paper for printers. As a necessary condition for visibility I on inkjet recording paper,
The ink is absorbed quickly into the paper, the ink that adheres to the paper is absorbed into the inner layer of the paper, the ink dots do not spread across the paper, the density of the ink dots on the paper is high, and the recording material lasts for 1 minute. stomach

[It is required to have water resistance and light resistance. However, among these ink sheets 1 to f4 required for recording paper, the actual situation is that the recording paper that satisfies water resistance and light resistance ↑1 at the same time is t'4<'. . ”: Many proposals have been made for inkjet recording paper related to writing. Example λbo, Japanese Unexamined Patent Publication No. 1983
-8499February proposed a surface-coated 1-paper coated with a polycationic polymer electrolyte such as polyvinyl pyridium bromide, January - tyreneimine, etc. -2- Unpublished Il! '157-102391M is a surface I coated with a resin such as polyvinylpyrrolidone, polyvinylviny[1-lydone/vinyl acetate copolymer, water-soluble emulsion, etc.] alone or in a mixture as a binder for surface coating.
Suggest I paper. JP-A No. 57-182445 discloses a crosslinking method by inkjet recording with water-based ink on a recording sheet containing polyvinyl alcohol or its derivative, heating the recording sheet, and dehydrating the polyvinyl alcohol or its derivative in the sheet within the molecule. Suggested. Japanese Unexamined Patent Publication 1987-
No. 191084 discloses an intermediate layer consisting of a water-absorbing resin and a polymeric binder on a base material, and a polymeric binder having dye adsorption properties such as polyvinylpyridine, polyacrylic acid, positive starch, etc. as the main agent. We propose a surface-coated T-paper with a top layer that protects the surface. Tokukai Akira! i8-5! i28 March proposed surface-coated T-paper that contained light calcium carbonate as a pigment and used a mixture of hydroxyethyl cellulose and polyvinylpyrrolidone as a binder. All of these proposals are good in terms of water resistance, but are not satisfactory in terms of light resistance. -3- Moreover, JP-A-57-87987 proposes a width containing at least one of metal oxides, metal chlorides, or tannic acid such as phosphotungstic acid, phosphomolybdic acid, and dichromium chloride. JP-A No. 57-87988 proposes the inclusion of ultraviolet absorbers such as 2-hydroxy-4-octoxybenzophenone and phenylsalidylic acid. Japanese Unexamined Patent Publication No. 1983
-87989 proposes to include antioxidants such as methylhydroquinone and hyde[l-quinone. These suggestions are
All of them have good light resistance, but are unsatisfactory in terms of water resistance. A general method for improving the light resistance of recorded matter is to select and use dyes with excellent light resistance for use in inkjet inks. However, the ink used for inkjet must satisfy certain conditions, such as not solidifying to avoid clogging the nozzles, not changing its hue over time, and not changing its physical properties such as viscosity and surface tension over time. Must be. However, although direct dyes and durable dyes R1 are generally used as dyes in inkjet inks, recorded materials using inks containing these dyes have problems in light resistance. An object of the present invention is to provide a high-performance inkjet recording paper that satisfies especially water resistance among the eleven conditions for inkjet recording and does not impair the emitted light r[. These purposes are direct dyes and acid f1
It has been discovered that by bringing a dye into contact with a specific polyethyleneimine quaternary ammonium compound on recording paper, a recorded matter with excellent water resistance and light resistance can be obtained. The present invention deals with the reaction of polyethyleneimines and halogenated hydrocarbons or the reaction of polyethyleneimines with halogenated hydrocarbons on a base paper.
Reaction with codonic acid followed by reaction with alkylene oxide,
or at least one of the polyethyleneimine quaternary ammonium compounds obtained by the reaction of polyethyleneimines with an alkylene oxide and a halogenated hydrocarbon.
The present invention relates to an inkjet recording paper characterized by being provided with a coating layer containing a seed, an antioxidant, and/or an ultraviolet absorber. -5- The polyethyleneimine quaternary ammonium compound of the present invention is produced, for example, by the following method. [1] Method of reacting polyethyleneimines with halogenated hydrocarbons [2] Method of reacting polyethyleneimines with protonic acid and then reacting with alkylene oxide ■ After reacting polyethyleneimines with alkylene oxide, A method of reacting halogenated hydrocarbons. Among the products obtained by these methods, those that give particularly good effects have the general formula (1) ) (wherein mt, tO or an integer of 1 or more, n is an integer of 1 or more, R+ is hydrogen , an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, a hydroxyalkyl group having 2 or more carbon atoms, R2 and R3 each have 1 to 20 carbon atoms
an alkyl group having 6 or more carbon atoms, an aryl group having 6 or more carbon atoms, a hydroxyalkyl group having 2 or more carbon atoms, and X represents a halogen atom, an inorganic protonic acid residue, or an organic protonic acid residue. ) is a polyethyleneimine quaternary ammonium compound represented by the structural unit. The reaction between polyethyleneimines and halogenated hydrocarbons is carried out at a temperature of room temperature to 200°C, preferably 40 to 150°C,
normal pressure to 20 g/cdG, preferably normal pressure to 10 K]/
It can be carried out within the pressure range of cJG. The reaction between polyethyleneimines and protonic acid occurs at room temperature ~
This can be carried out at 100°C and normal pressure. The reaction between polyethyleneimines and alkylene oxide is carried out at a temperature of 20 to 200°C, preferably a concentration of 30 to 100°C, normal pressure to 20 islands/cdG, preferably normal pressure to 10K).
This can be done in a pressure range of 10 tfG. -7- As the polyethyleneimine, polyethyleneimine or a modified polyethyleneimine is used. The polyethyleneimine used here has a molecular weight of 100 to i, ooo, o
oo, preferably 300 to 200,000. In addition, modified polyethyleneimine can be used to convert polyethyleneimine into aldehydes, halogenated hydrocarbons, isocyanates,
Examples include partially modified compounds such as urea and acids. The alkylene oxide may be one or more of ethylene oxide, propylene oxide, isobutylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, hexene oxide, styrene oxide, etc., and the sequence is grafted. It may be of type, block type and/or random type.Also, any one may be added first.A copolymer of ethylene oxide and propylene oxide is particularly preferred.The molecular weight of the polyether to be added is 600. ~5,000,000. Examples of protonic acids include hydrochloric acid, perchloric acid, sulfuric acid, sulfurous acid,
No phosphoric acid, phosphorous acid, hypophosphorous acid, nitric acid, -8-boric acid, hydroiodic acid, etc.n, formic acid, acetic acid, propionic acid, oxalic acid, lactic acid, malonic acid, citric acid, phthalic acid , maleic acid, fumaric acid, succinic acid, p-toluenesulfonic acid, adipic acid, sorbic acid, trimellitic acid, pyromellitic acid, acrylic acid, methacrylic acid, glutaric acid, sebacic acid, terephthalic acid, etc. can be mentioned. Examples of halogenated hydrocarbons include methyl chloride, ethyl chloride, methyl bromide, ethyl bromide, methyl iodide, ethyl iodide, ethylene chlorohydrin, bichlorohydrin, ethylene bromohydrin, monochloroacetic acid, benzyl chloride, 1, Examples include 2-dichloroethane, 1,3-dichloropropane, 1,2-dichlorobutane, and the like. Antioxidant 11-agents include phenol-based, monophenol-based,
Examples include bisphenol-based, polymeric phenol-based, sulfur-based, and phosphorus-based compounds, as well as erythorbic acid, ascorbic acid, and derivatives thereof. Examples of phenolic antioxidants include 2,6-di-tert-butyl-
p-cresol, -9-butylated hydroxyanisole, 2.6-t-butyl-
Examples include 4-ethylphenol, stearyl-β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and the like. Examples of bisphenol antioxidants include 2,2'-methylene-bis-(4-methyl-6-tert-butylphenol) and 2,2'-methylene-bis-(4-ethyl-6-tert-butylphenol). ), 4,4'-thiobis-(3-methyl-6-tert-
butylphenol), 4.4'-butylidene-bis-
(3-methyl-6-tert-butylphenol) and the like. As a polymeric phenolic antioxidant,
For example, 1,3.5-t-rimedil-2,4,6-1-
Lis(3,5-di-tert-ablu-4-hydroxybenzyl)benzene, tetrakis-[methylene-3-(3'
, 5'-di-tert-butyl-4'-hydrocyphenyl)propy, 4-nate] methane, bis[3,3'-bis-(4'-hydroxy-3'-1-butylphenyl)
Examples include butyric acid 1-glycol ester, tocopherol-10-ol, and the like. Examples of the 1IiIt yellow antioxidant include dilaurylthiodipropionate-1-, dimyristilbuA dipropionate, distearyldiA dipropionate, and the like. Examples of phosphorus-based antioxidants include 1~rifhenyl phosphite, phenyl diisodecyl bosphite 1~, cyclic Δbentamp trirubys Ll ctadecylbosphite),
Examples include 1-lith(nonyl phenyl) phosphite 1, tris(mono, dinonylphenyl) phosphite 1 and so on. Others erythorbic acid (or Na salt), dibutylhydroxytoluene, dl-α-1 hecopherol,
nordihydroguaiaredic acid, butylated hydroxyanisole, 1-ascorbic acid (or Na salt), L-ascorbic acid stearate, isoascorbic l! I (or Na salt), propyl gallate, hydroquinone, methylhydroquinone, hydroquinone dimethylnityl, diphenylamine, pyrogallol, and the like. Among these antioxidants, water-soluble antioxidants are preferred. Among them, -11- is preferably L-ascorbic acid (or Na salt), isoascorbic acid (or Na salt), and the like. The amount of the antioxidant used is preferably 0.01% by weight or more, particularly 0.01% by weight or more based on the polyethyleneimine primary ammonium compound. Examples of the ultraviolet absorber include salidylic acid-based, benzophenone-based, penzotriazol-based, and cyanoacrylate-based compounds. As for salidylic acid-based ultraviolet absorbers,
Examples include phenyl salicylate, p-tert-butylphenyl salicylate-1, ρ-Δcutylphenyl salicylate 1 and so on. As a bensiphenone ultraviolet absorber, even 1;
, 2.4-dihydroxybensif Jone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4
-Octoxybencyphenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,47-simethoxybenzophenone, 2-hydroxy- 4-methoxy-5-sulfobenzophenone,
Examples include 2°-12-2'-dihydroxy-4,4'-dimethoxy-5-sulf A bensif I non Na salt. Examples of benzotriazole-based ultraviolet absorbers include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-5
'-tert-butylphenyl)benzo1-lyazole, 2-(2'-hydroxy-3'.5'-di-tart-butylphenyl)benzotriazole, 1-(2'-hydroxy-3'-tert-butyl -5'-methylphenyl)-5-chlorobenzotriazole, 2- (2'-hydroxy-3',5'-
di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3', 5
'-di-tert-amylphenyl)benzo1-lyazole, 2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole, and the like. For example, cyanoacrylate ultraviolet absorbers include 2
-edylhexyl 2-cyano-3,3'-diphenylacrylate, ethyl-2-cyano-3,3'-diphenylacrylate, and the like. Among these ultraviolet absorbers, water-soluble 2-human[]]xy4-me]~xy5
-Sulfobenzofunone, 2,2'-dihydroxy-
4,4'-dime-1-''-cy-5-sulfA benzophenone Na salt and the like are preferred. The amount of ultraviolet absorber used is 0.01% by weight or more, especially 0.01% by weight based on the polyethyleneimine primary ammonium compound.
1 weight h1% or more is preferable. The paper of the present invention is treated with a polyethyleneimine quaternary ammonium compound to form a coating layer. The aqueous solution is applied by coating, dipping, spraying, etc. Application is performed using a size press, gate roll, roll coater,
Equipment such as a blade coater, an air knife rotor, a gravure coater, a bar coater, a flash coater, a cheongyang Grex coater, a curtain coater, etc. can be used. Application amount is 0.01-10g/l11
2, particularly preferably in the range of 0.1 to 2o/f-14=. For drying after treating paper with polyethyleneimine quaternary ammonium compound, use methods such as natural drying at room temperature, oil bath, gas heater, electric heater, steam heating heater, hot air drying, infrared drying, drum dryer, etc. be able to. The coating solution containing the polyethyleneimine quaternary ammonium compound, antioxidant and/or ultraviolet absorber of the present invention can be used by coating it after the papermaking process, or by coating commercially available paper with the polyethyleneimine quaternary ammonium compound, antioxidant and/or ultraviolet absorber. Any method such as coating with a coating liquid containing a UV absorber and/or an ultraviolet absorber can be employed. When treating with a solution containing a polyethyleneimine quaternary ammonium compound, an antioxidant, and/or an ultraviolet absorber, water-soluble polymers, thickeners, surfactants, antifoaming agents, etc. can be combined. The paper of the present invention can be used for coated printing paper such as plain paper, paper, coated paper, lightweight coated paper, cast coated paper, Infusiera 1-recording paper, printing paper, packaging paper, etc. Either medium-quality paper such as trade paper, magazine, or newspaper, or cell [1-space fiber] such as pulp can be used. Further, pigments, binders, dispersants, antifoaming agents, lubricants, preservatives, flow modifiers, etc. are contained in these as necessary. The dyes used in the ink for inkjet 1 of the present invention include direct dyes, acid dyes, mordant dyes, metal salt dyes, vat dyes, disperse dyes, fluorescent dyes, etc. In particular, direct dyes,
Dyes such as acid dye *Mi 1 are preferably used. Specific examples include the following dyes. [1] Direct dyeing C, 1, D 1rect Red 75 (C,, 1,
25380) C, 1, D 1rect Red 79
(C, T, 29065) C, 1, Direct Red
80(C,l 29225)CJ,D 1rect
Yellow 27 (C, 1, 13950) C, 1,
Direct Yellow 28 (C, 1, 1955
5) C, 1, Direct Yellow 33 (C,
1,29020)C,1,D 1rect Blue
71 (C,1,34140)C,1,Direct
Blue 76 (C, 1, 24411) -16- C, 1, D 1rect RIue 86 (C, 1,
174180) [2] Acid dye C, 1, △cid Red 32 (C, 1, 17065
)c, r, △cid Red 37(C,1,17
045>C,1,Ac1d Red 87(C,1,4
5380) c, r, △aid Y el low 2
3 (C,1,119140)C,1,Ac1d Ye
low 29 (C, 1, 18900) C, 1, Ac1
d Yellow 38 (C, 1, 25135) C, 1
, Ac1d Blue 29 (CJ, 20460)C
,1,Ac1d V 1olet 34 (C,1,6
1710) C, 1, Ac1d Black 52 (C,
1,15711> The present invention will be explained in more detail with reference to the following examples, but the present invention is not limited to these examples. In the examples, parts are parts by weight, and % is weight %. O evaluation method 1) Paper used - 17 - Plain paper with size 1 good for 25 seconds by Sudekihi method 2) Coating method and coating amount Prepare a 1% by weight aqueous solution of each coating amount H, and use a bar coater. Approximately 0.2 to 1 q/m2 was applied. 3) Printing method: Using an inkjet nozzle (nozzle diameter 50μ),
One inkjet printer prints cyan, magenta, and yellow. 4) Peeling of the recording layer when water-resistant inkjet recording paper is immersed in water for 10 minutes and the recording layer is rubbed with a finger. ○ No plagiarism at all. △ No peeling. × There is peeling. 5) Lightfastness The inkjet recording paper was exposed to a carbon arc (Shimadzu Fade Tester CF-2ON) for about 5 to 24 hours. 0 Fading pox equivalent to untreated paper. Δ Discoloration almost equivalent to untreated paper. X: Degree of fading greater than that of untreated paper. A preparation example of the polyethyleneimine quaternary ammonium compound used in the present invention is shown below. [1] Polyethyleneimine quaternary ammonium compound] In a stainless steel autoclave equipped with a stirrer, a 30% by weight aqueous solution of polyethyleneimine (manufactured by Nippon Shokubai Chemical Co., Ltd., trade name Epomin 5P-012, molecular weight 1200).
Prepare 100 parts by weight, temperature 90~100℃, pressure 1~
5Ki10 (70 parts by weight of methyl chloride was supplied with G and the reaction was carried out for 5 hours. The product thus obtained is referred to as a polyethyleneimine quaternary ammonium compound). [2] Polyethyleneimine No. 4 @ Ammonium compound〇-19- In a stainless steel t-1-crepe equipped with a stirrer,
100 parts by weight of a 30% aqueous solution of polyethyleneimine (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., trade name: Evomin 5P-012, molecular weight 1200) and 4/1 part by weight of nitric acid were charged at a temperature of 90 to 100°C and a pressure of 1. ~5 K9/ci
70 parts by weight of propylene oxide was supplied using G, and the reaction was carried out for 5 hours. The product thus obtained is referred to as a polyethyleneimine quaternary ammonium compound (B). 0] Polyethyleneimine quaternary ammonium compound C
] In a stainless steel A-crepe equipped with a stirrer, a 301% aqueous solution of polyethyleneimine (Nippon Shokubai Chemical Co., Ltd.), trade name 1 Bomin 5P-012, min. nil 20
0) Add 100 parts by weight and heat to 1160~70. 'C1
30 parts by weight of ethylene oxide and 65 parts by weight of epichlorohydrin were supplied at a pressure of 1 to 51e10ilG, and the reaction was carried out for 3 hours. The product thus obtained is referred to as polyethyleneimine quaternary ammonium compound (2). -21- In the table *I PEI: Polyethyleneimine (molecular weight 1200) *2 Antioxidant 1 agent: L-sodium ascorbic acid *3 Ultraviolet absorber: 2.2'-hydroxy-4,4
'-Dimethoxy-5-sulfoperezophenone Na salt Patent applicant Nippon Shokubai Kagaku Kogyo Co., Ltd. -23- -ζ67-

Claims (1)

[Scope of Claims] [1] On a base paper, a reaction between polyethyleneimine and a halogenated hydrocarbon, or a reaction between polyethyleneimine and a pro-1-chloric acid and then a reaction with an alkylene oxide, or polyethylene A coating layer containing at least one polyT tyrene imine quaternary ammonium compound obtained by the reaction of imines, alkylene oxides, and halogenated hydrocarbons, an antioxidant, and/or an ultraviolet absorber is installed. Inkjet recording paper.