JPS6076386A - Ink jet recording paper - Google Patents

Abstract

PURPOSE:To satisfy water resistance without damaging light-resistance by forming an applying layer containing at least one kind of compound selected from a specific polyethylene imine quarternary ammonium compound on base paper. CONSTITUTION:(A) Polyethylene imines and hydrocarbon halide are reacted and a polyethylene imine quarternary ammonium compound is obtained. (B) Polyethylene imines and proton acid are reacted, alkylene oxide is reacted, and the polyethylene imine quarternary ammonium compound is acquired. (C) Polyethylene imines and alkylene oxide and hydrocarbon halide are reacted, and the polyethylene imine quarternary ammonium compound is obtained. An applying layer containing one kind or more of said polyethylene imine quarternary ammonium compounds is formed on base paper, and ink jet recording paper is acquired.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a 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.

The recording method used in inkjet is suitable for facsimiles and various printers because it produces less U noise, can perform high-speed recording, can print in multiple colors, and can use high-quality paper, medium-quality paper, and plain paper. It is used in a wide range of fields such as recording paper.

The requirements for inkjet recording paper are that the ink is quickly absorbed into the paper, that the ink adhering to the paper surface is absorbed into the inner layer of the paper, that the ink dots do not spread on the paper surface, and that the ink drive on the paper surface is fast. It is required that the recorded material has a high resistance to water and light resistance of 1 minute. However, the reality is that it is not possible to obtain a recording paper that satisfies water resistance and light resistance at the same time among the requirements for inkjet recording.

Ink related to the above]: 1~Regarding recording paper,
Many proposals have been made so far. For example, JP-A-5
No. 6-84992 proposes a surface-coated paper coated with a polycarb-A polymer electrolyte such as polyvinyl, pyridium, bromide, or polyethyleneimine.

JP-A-57-102391 proposes Surface 41 paper coated with 144 or a mixture of resins such as polyvinylpyrrolidone, polyvinylpyrrolidone/vinyl acetate copolymer, and water-soluble emulsion as a binder for surface coating. JP-A No. 57-182445 discloses that after ink jet recording is performed on a water-based ink on a recording sheet I containing polyvinyl alcohol or its R conductor, the recording sheet is heated, and the polyvinyl alcohol or its derivative in Sea 1 is heated. We proposed a crosslinking method using intramolecular dehydration. JP-A-57-1
91084@ has 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. -3- We propose Surface 41 paper with the outermost layer containing () as the main ingredient.

JP-A-58-55283 proposes a surface-coated paper containing light calcium carbonate as a pigment and using a mixture of hydroxyedyl cellulose and polyvinylpyrrolidone as a binder. All of these proposals are good in terms of water resistance, but are they a whirlpool in terms of secondary light f-no-1? It's not something you can control.

Also, Tokukai Akira! No. 17-87987 discloses at least one of metal oxides such as phosphotungstic acid, phosphomolybdic acid, dichromium chloride, gold m chloride, or tannic acid.
It is proposed to include one. JP-A No. 57-87988 is 2-
It is proposed to include ultraviolet absorbers such as human ``1xy-4-71 ctoxybenzofone'' and phenylsalidylic acid. JP-A-57-87989 proposes to include antioxidants such as medylhydro[]quinone and hydroquinone. Although these proposals are good in terms of light resistance, they are not satisfactory in terms of water resistance.

A general method for improving the light fastness of recorded matter is to select and use a dye with an excellent light fastness of -4- as the dye used in inkjet ink. However, the ink used for inkjet must satisfy 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, direct dyes and acid dyes are commonly used as dyes for 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 water resistance among the various conditions required for inkjet recording and does not impair light resistance.

For these purposes, it was discovered that by bringing direct dyes and durable dyes into contact with specific polyethylenimine modifications on recording paper, recordings with excellent water resistance and light resistance can be obtained.

In the present invention, on a base paper, (4) a polyethyleneimine 11th class ammonium compound obtained by reacting polyethyleneimines with a halogenated hydrocarbon; At least one compound selected from the following: a polyethyleneimine eleventh-class ammonium compound obtained by reacting a polyethyleneimine with an alkylene oxide; Scale polyethyleneimine No. 4
The present invention relates to an inkjet recording paper characterized by being provided with a coating layer containing an ammonium compound.

The polyethyleneimine quaternary ammonium compound of the present invention is produced, for example, by the following method.

[1] Method of warping polyethyleneimines and halogenated hydrocarbons [2] Method B of reacting polyethyleneimines with protonic acid and then reacting with alkylene oxide -6- Method B] Polyethyleneimines and alkylene oxide A method in which a halogenated hydrocarbon is reacted after the reaction.

Among the products obtained by these methods, those having particularly good effects are those of the general formula [1] X0R.

(In the formula, m is an integer of 0 to 1 or more, n is an integer of 1 or more, R+ is hydrogen, an alkyl group having 1 to 20 carbon atoms, 6 carbon atoms
The above aryl group, hydroxyalkyl group having 2 or more carbon atoms, R2 and R3 are 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, and X is a halogen atom or an inorganic represents a protonic acid residue or an organic protonic acid residue. ) is a polyethyleneimine 4-7-class 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 ~ 2 OK! J/rnG, preferably normal pressure to 10Kt
/lfG.

The reaction between polyethyleneimines and protonic acid occurs at room temperature ~
It can be carried out under 100'C1 normal pressure.

The reaction with alkylene oxide such as polyethyleneimine is carried out at a temperature of 20 to 200°C, preferably 30 to 100°C.
Normal pressure to 20 Ki/CI (G, preferably normal pressure to 10Ki
/cJG pressure range.

As the polyethyleneimine, polyethyleneimine or a modified polyethyleneimine is used. The polyethyleneimine used here has a molecular weight of 100 to 1,000□00
01 is 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 A oxide, 1,2-butylene oxide, 2,3-butylene oxide, hexene oxide, styrene oxide, etc., and its arrangement is graft type, block type, etc. Either type and/or random type may be used. Moreover, either one may be added first. Particularly preferred is a copolymer of ethylene oxide and propylene oxide. The molecular weight of the polyether obtained ranges from 600 to 5,000,000.

Protonic acids include hydrochloric acid, perchloric acid, sulfuric acid, sulfite,
Inorganic acids such as phosphoric acid, phosphorous acid, hypophosphorous acid, nitric acid, boric acid, hydroiodic acid, formic acid, acetic acid, propionic acid, oxalic acid, lactic acid, malonic acid, citric acid, phthalic acid, maleic acid, Fumaric acid, succinic acid, o-t-luenesulfonic acid,
Examples include organic acids such as adipic acid, sorbic acid, trimellitic acid, pyromellitic acid, acrylic acid, methacrylic acid, glutaric acid, levacic acid, and terephthalic acid.

-9- Examples of halogenated hydrocarbons include methyl chloride, ethyl chloride, methyl bromide, ethyl bromide, methyl iodide, ethyl iodide, ethylene chlorohydrin, bichlorohydrin, ethylene bromohydrin, monochloroacetic acid, and benzyl chloride. , 1,2-dichloroethane, 1,3-dichloropropane, 1,2-dichlorobutane, and the like.

The method of treating the paper of the present invention with a polyethyleneimine quaternary ammonium compound to form a coating layer includes treating the paper with a polyethyleneimine quaternary ammonium compound of 0.01% by weight or more,
Preferably, an aqueous solution of 0.1% by weight or more is applied by coating, dipping, spraying, or the like.

Apparatuses such as a size press, a gate roll, a 1-roll roll, a blade coater, an air knife coater, a gravure coater, a bar coater, a flash coater, a chamber coater, a kerf coater, etc. can be used for coating. Application amount is 0.01-10a/l,
In particular, it is preferably in the range of 0.1 to 2 o/g.

-10- Dry the paper after treating it with the polyethyleneimine quaternary ammonium compound by air drying at room temperature or by using an oil stove,
gas heater, electric heater, steam heater,
Methods such as hot air drying, infrared drying, drum dryer, etc. can be employed.

The mode of use of the polyethyleneimine quaternary ammonium compound of the present invention is to apply the polyethyleneimine quaternary ammonium compound after the papermaking process and then treat the paper, or to apply the polyethyleneimine quaternary ammonium compound to commercially available paper. Any method for treating paper can be employed.

When treating with the polyethyleneimine quaternary ammonium compound, water-soluble polymers, thickeners, surfactants, antifoaming agents, antioxidants, ultraviolet absorbers, etc. can be added as necessary.

The paper of the present invention is coated printing paper such as plain paper, art paper, coated paper, lightweight coated paper, and cast coated paper, high-quality paper used for inkjet recording paper, printing paper, packaging paper, etc., magazines, and newspapers. Either medium-quality paper or pulp such as Lerulose 11iIII 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 inks for Infusiella 1 to 1 of the present invention include direct dyes, acid dyes, mordant dyes, metal complex dyes, vat dyes, disperse dyes, fluorescent dyes 1, etc. In particular, direct dyes, acid dyes, etc. dyes are preferably used. Specific examples include the following dyes.

[1] Direct dyeing C, 1, D 1rect Red 75 (C, 1, 2
5380) C, 1, D 1rect Red 7'J
(C, T, 29065) C, 1, Direct Red
80 (C, 1, 29225) C, I', Direct
Yellow 27 (C, 1, 13950) C, 1,
Direct Yellow 28 (C, 1, 1955
5) C, T, D treat Yellow 33 (
C,1,29020)C,1,Direct Blue
71 (CJ, 34140) CJ, D 1rect 1
31ue γ6(C,I,24411)C,1,Di
rect Blue 86 (C, 1, 174180) -
12- (2) Mt! l stain I C, T, Δcid Red 32 (0,117065
) CJ, Ac1d Red 37 (C, 1, 17045
)C,1,△cid Red 87 (C,1,453
80) CJ, △cid Y el low 23 (C
,1,119140)C,1,△cid Yel lo
w 29 (C,118900)C,1,AcidYe
low 38(C,l 25135)C,1,△c
id B blue 29 (C, 1, 20460)C,
1, Δc'id V 1olet' 34 (C, 1,
'61710)C,L Ac1d Black 5
2(C,l 15711 ) The present invention will be briefly explained by the following Examples, but the present invention is not limited to these Examples. In addition, in the examples, parts represent parts by weight, and % represents weight %.

The evaluation method in Examples and Comparative Examples was performed according to the method specified below.

○Evaluation method 1) Paper used -13- plain paper with a sizing degree of 25 seconds by the Steckicht method 2) Coating method and coating amount Prepare a 1% by weight aqueous solution of each coating sample, and use a bar coater to coat approximately 0.2% by weight. ~1(+/Tll' was applied.

3) Printing method ゛Equipped with an inkjet nozzle (nozzle diameter 50μ),
An 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 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.

Degree of color fading equivalent to O-untreated paper.

-14- X: Discoloration of untreated paper-1.

An example of preparing the polyethyleneimine quaternary ammonium compound used in the present invention is shown below.

[1] Polyethyleneimine quaternary ammonium conversion In a stainless steel A-1 crepe equipped with a stirrer, a 30% by weight aqueous solution of polyethyleneimine (Nippon Shokubai Kagaku Kogyo I
Manufactured by NO, trade name Evomin 5P-012, molecular weight 1200
) 100 parts by weight, temperature 90-100℃, pressure 1
~5 was supplied with 70 parts by weight of methyl chloride at 9/cy#G,
The reaction was carried out for 5 hours. The product thus obtained was converted into polyethyleneimine quaternary ammonium (2) polyethyleneimine quaternary nonammonium compound CB) in a stainless steel crepe equipped with a stirrer. 100 parts by weight aqueous solution (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., trade name: EBOMY 15-N 5P-012, molecular weight 1200):
44 parts by weight of dichloromethane and nitric acid were charged, and 70 parts by weight of propylene oxide was supplied at a temperature of 90 to 100° C. and a pressure of 1 to 5 μ/ff1G, and the reaction was carried out for 5 hours. The product obtained in this way was converted into polyethyleneimine quaternary ammonium using a stainless steel I! equipped with a stirrer for polyethyleneimine quaternary ammonium conversion. l; In a dt-crepe, add a 30 wt % aqueous solution of polyethyleneimine (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., trade name Evomin 5P-012, molecular weight 1.2
00) Prepare 100 parts by weight and heat at 60 to 70'C.
, Pressure Horn 1-5D10 (30 parts by weight of ethylene oxide and 65 parts by weight of epichlorohydrin were supplied in G, and the reaction was carried out for 3 hours. The product obtained in this way is referred to as polyethyleneimine quaternary ammonium compound C). .

−　16　− Table-1 Patent applicant Nippon Shokubai Kagaku T Gyo Co., Ltd. - 17 -

Claims (1)

[Scope of Claims] [1] Basic composition 2) A polyethyleneimine quaternary ammonium compound obtained by reacting polyethyleneimine with a halogenated hydrocarbon; C) a polyethyleneimine quaternary ammonium compound obtained by reacting polyethyleneimines with an alkylene oxide and a halogenated hydrocarbon; An inkjet recording paper comprising a coating layer containing a polyethyleneimine quaternary ammonium compound.