JPS6046288A - Ink jet recording method - Google Patents

Abstract

PURPOSE:To contrive to enhance color tone, preservability and water resistance, by using an ink which comprises a monoazopyrazolone dye and a recording medium which comprises at least one of a water-soluble salt of an at least bivalent metal, a polyamine, an alkylamine salt and a quarternary ammonium salt. CONSTITUTION:A mixture of a monoazopyrazolone dye of the formula, water and other additives is dissolved by agitating with heating, and is filtered to prepare an ink. A composition containing at least one of a water-soluble salt of an at least bivalent metal, an alkylamine salt, a polyamine and a quarternary ammonium salt is applied to a base provided with a surface coat layer, is dried, and the resultant material is subjected to hot press calendering to produce a recording medium. accordingly, color tone of a yellow color, light resistance and water resistance are enhanced.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to an inkjet recording method, and particularly to an inkjet recording method using yellow ink.

Prior Art In recent years, in the field of inkjet recording technology, technological development for the reproduction of color images has been actively carried out, and various studies have also been conducted on inks for reproducing images of the three primary colors, cyan, magenta, and yellow. ing. Ink is required to have various quality characteristics, but yellow ink has not yet been found to have excellent color tone and image storage stability, especially water resistance.

Conventionally, in order to solve these drawbacks, various efforts have been made to improve the color tone by performing color correction, and to improve the composition of the ink, especially the selection of dyes, as well as the recording medium (although various efforts have been made to The current situation is that we have not reached a satisfactory result.

Purpose The present invention aims to solve the above-mentioned drawbacks, namely, in the field of inkjet recording technology, it is possible to reproduce a yellow image with a sufficiently satisfactory tone, and to improve the tone and storage stability of the image, especially water resistance. The purpose of this invention is to provide an inkjet recording method with excellent properties.
- It has been discovered that a combination of an ink containing a dye and a recording medium treated with a specific material is sufficiently effective, leading to the present invention. That is, the inkjet recording method of the present invention
Ink containing pyrazolone dye, water-soluble metal salt of divalent or higher valence metal, polyamine, alkylamine salt, and 4
The present invention is characterized in that it uses a recording medium containing at least one type of ammonium salt.

Although various monoazo-pyrazolone dyes can be used, it is particularly preferable to use those represented by the following general formula.

R1: hydrogen atom, -805M, alkyl group, hydroxy group R2: alkyl group, -COOM, -8o, MR6: hydrogen atom, alkyl group, -805M, hydroxy group, -CO
OM, halogen group m:'n: an integer M+ of either O, L L 3:
In the alkali metal, amine cation, and ammonium ion R1-R3, the sum of -8O,M and -CO(5''M) is at least two.

In addition to the above dye and water, the ink used in the inkjet recording method of the present invention can contain various additives depending on the purpose, such as a wetting agent and a preservative and fungicide.

The content of the dye represented by the above general formula is suitably 05 to 30% by weight, preferably 15 to 6% by weight, based on the ink. Specific examples of the dye are listed below.

503M 5qN 05M 5O included (O3M Wetting agents include, for example, polyhydric alcohols and alkyl ethers of polyhydric alcohols.
0% by weight can be used.

A specific example is shown below.

Polyhydric alcohol> Ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, glycerin,
Polyethylene glycol (20-5OO), polypropylene glycol, etc. <Alkyl ethers of polyhydric alcohols> Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether monomethyl ether, triethylene glycol monoethyl ether Among these wetting agents, a mixture of glycerin and diethylene glycol is preferred in the recording method of the present invention, such as ethyl ether, which has stable performance even after the ink has been left for a long period of time. 1
Those having a value of 115 to 115 are particularly preferred.

In the present invention, the above-mentioned other wetting agent may be further added to the mixture, and in this case, it is preferable to add the wetting agent at an upper limit of about 40% by weight based on the total amount of the wetting agent.

As the preservative and antifungal agent, for example, sodium dehydroacetate, sodium thiosulfate, ammonium thioglycolate, organic nitrogen sulfur compounds, etc. can be used.

Furthermore, if necessary, the following compounds which are particularly effective as dye solubilizers can be added.

Amino compounds such as triethanolamine; Nitrogen-containing polycyclic compounds such as N-methyl-2-pyrrolidone and 2-pyrrolidone 1,3-diethylimidazolidinone; Intermolecular esters of oxycarboxylic acids such as valerolactone and caprolactone Compound: Calsolve acetate compound such as ethylene glycol monomethyl ether acetate The recording method of the present invention can achieve the intended purpose by combining the ink described below with the following specific recording medium. . The recording medium will be explained below.

The recording medium used in the present invention contains at least one of water-soluble metal salts of divalent or higher valence metals, alkylamine salts, polyamines, and quaternary ammonium salts. There are (1) those in which a coating layer containing such a treatment agent is provided, and (2) those in which the treatment agent is impregnated into the substrate without providing a particular coating layer. The content of the processing agent, regardless of the type of processing agent,
(In the case of 11, better results can be obtained by increasing the number slightly than in the case of (2).

In the present invention, one or more water-soluble metal salts of divalent or higher valence metals are added in amounts of 0.2 f//d or more, preferably Lot//
rr? Above 8. (Contained at a ratio of 1/rrl' or less. Specific examples of the metal salt are shown below.

(Divalent metal salt) M9C/2, CaBr2, Ca (NO
3) 2, CaI2.

ZnC/2, ZnBr2, ZnI2, Zn (C103
)2.

Zn804, Zn(NO3)2, 8rI2, SrBr2
.

SrC/2. Sr(NO3)2, BaC/2, Ba (
NO3)2.

Ba(OH)2, BaI2. BaBr2,F
e (NO3) 2.

Ni CNOs) 2 , Ni (804) , Ni
C/2, CuC12.

u804 (Trivalent metal wholesaler A/C/3.A/2 (SO2) g.A/
(NOx)2,Secl! x.

Sc(N05)a. 8e2(804)s,Ga(NO3
)S.

GaC/3. Ga2(804)a,InC/3,Fe(
NO5)5.

Various alums (tetravalent metal #D TiC/4, GeC/4+Zr (80
4) 2,8nC/4.

an (804) 2, Pb (CH3COO
) 2 Among these specific examples, A/C/II IA/(804) s, A/(NO
5) 5, ZnC/2, ZnSO4.

Snc14, CaC/2, MyC/2, In
C/a is particularly preferred.

The alkylamine salt has a flow rate of 0.05 f//d or more and a current of 0.05 f//d or more.
From 2f//d5. It is preferable to contain less than Oy/rn'. A specific example is shown below.

Decylamine acetate, undecylamine acetate.

Dodecylamine acetate, tridecylamine acetate.

Tetradecylamine acetate, pentadecylamine acetate.

Hexadecylamine acetate, heptadecylamine acetate.

Octadecylamine acetate, nonadecylamine acetate.

Eicobucylamine acetate or the hydrochloride polyamine of the above alkylamine is o, osf//rr? Above, special tc0.
1@/m1 or more 4. It is preferable to contain less than Oy/rn'.

A specific example is shown below.

The content of quaternary ammonium salts such as polyamide polyamine, polyoxyethylene alkylamine, polyethylamine-epichlorohydrin, polydimethylaminoethyl methacrylate, or polyalkylammonium is preferably 0.15'/m' or more. A specific example is shown below.

Among recording media such as lauryltrimethylammonium bromide or chloride, cetyltrimethylammonium bromide or chloride, octaisoquinolium bromide or chloride, and hexadecyltrimethylammonium bromide or chloride, those in which the substrate is directly impregnated with the above-mentioned processing agent are explained below. For example, plain paper, no-size paper, water-absorbing plastic film, or the like is used as the substrate, and a solution or dispersion of the processing agent is immersed or coated thereon.

Next, a description will be given of a substrate provided with an upstream coating layer.The substrate may be, for example, cellulose-based paper, synthetic paper, plastic film, etc., regardless of the ink liquid absorption capacity.
Glass, metal plates or metal foils can be used.

The coating layer is formed from, in addition to the processing agent, a binder and, if necessary, additives such as pigments.

The binders used are broadly classified into A, resin type, and B, latex type, as shown below. In this case, it is preferable to use a binder that is a mixture of A and B because water resistance and the like are further improved.

A, water-soluble resin-based oxidized starch, etherified starch, esterified starch, dextrin, casein, gelatin, gum arabic, vegetable protein cellulose, carboxymethylcellulose, hydroxyethylcellulose, cellulose derivative, polyvinyl alcohol, polyvinylpyrrolidone, maleic anhydride resin , mixtures of one or several of vinyl acetate polymer, polyvinyl butyral, polyacrylamide, etc., mutual polymers of the above polymers, modified polymers, etc.

B, latex polyvinyl acetate polymer latex, styrene-isoprene copolymer latex, styrene-butadiene copolymer latex, acrylic polymer latex, acrylic-vinyl acetate copolymer latex, methyl methacrylate-butadiene copolymer latex Examples of pigments include modified products such as copolymers and mixtures of two or more of them, as shown below.

Clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, magnesium carbonate, magnesium sulfate, barium sulfate, titanium oxide, zinc oxide, zinc sulfide, zinc carbonate, tisane white, calcium silicate, aluminum oxide, aluminum hydroxide silicate , aluminum hydroxide,
Zeolite; preferably calcium carbonate, magnesium carbonate, diatomaceous earth, tisane white, etc. from the viewpoint of whiteness, dispersibility, and substance stability.

Various methods can be considered for forming the coating layer of the recording medium. A layer may be formed by applying a liquid containing an adhesive, an additive, and a processing agent to a substrate and then drying it.

To specifically explain method (1), a dispersion containing a binder and additives as main components is coated with a blade coating method, air knife coating method, roll coating method, wire bar coating method, spray coating method, gravure coating method, etc. It is applied to the substrate by a coating method, a reverse roller coating method, etc., and dried by hot air or heating, and the coating amount is from 01y/go to 609/rr? , preferably 39/rd to 20y/rr? A layer is formed, and then a liquid containing 0.1 t% to 30 wt% of a processing agent is applied using one of the above coating methods for layer formation, and dried to form a record used in the present invention. Get medium.

Furthermore, the recording medium obtained by the above method +l+ or (2) is heated at a temperature of, for example, 50°C to 200°C, preferably 6°C.
From 0℃ to 120℃, pressure 10/α to 150 9/(
'm, preferably from 50Ky/cyn to 80~/(1)
By performing calendering under these conditions, the properties of the recording medium can be further improved.

Next, the present invention will be explained by examples. All % here represents weight %.

Example 1 A mixture consisting of the following composition was heated and stirred at about 70°C for about 4 hours to dissolve, and a membrane filter with an opening diameter of 0.45 μm was prepared.
Then, ink (Al) was prepared.

Na salt of the dye of the specific example (1) 35% Diethylene glycol 12.5% Glycerin 50% Sodium hydroxide Slightly pure water Remaining amount After sufficiently dispersing the following composition using a ball mill dispersion method,
The solid content of the dispersion was 10 using the doctor blade method.
Coated on high-quality paper with a thickness of 100 mm at
A surface coating layer was formed by drying for a minute.

Charcoal or calcium powder 40% Polyvinyl alcohol 6% Water A 15% aqueous solution of aluminum chloride was applied to the remaining surface using an air knife coating method, with a solid content of 1 O5'/+tl', and after drying at 110°C for 10 minutes. , 80℃, 70Kp/
The recording medium (A
1 was created.

Example 2 A mixture having the following composition was stirred at 80°C for 3 hours to dissolve it.
Next, the mixture was filtered twice using a membrane filter with an opening diameter of 025 μm to prepare ink (B).

L+salt of the dye of the specific example (6) 4% glycerin 4
% Diethylene glycol 13% Sodium dehydroacetate 0.5% Pure water 65.5% On the other hand, after forming the surface coating layer on the recording medium of Example 1 (Al), Sanfix 555 manufactured by Sanyo Chemical Co., Ltd. was used instead of the aluminum chloride aqueous solution. A 3% aqueous solution of (polyamine) was coated by an air knife coating method at a solid content of 08y/n+', dried, and calendered to obtain a recording medium σ3).

Example 3 A mixture having the following composition was heated and stirred at about 70° C. for about 3 hours to dissolve, and then filtered through a membrane filter with an opening diameter of 025 μm to prepare ink (q).

Ammonium salt of the dye of the above specific example Q [l 3.5% diethylene glycol 22% glycerin 7% triethanolamine 3% Hokuside LX-2 (Shinyong Chemical Co., Ltd.) 03% pure water remaining amount Meanwhile, the following composition was subjected to ball mill dispersion method. After thoroughly dispersing the dispersion at 100°C, the dispersion was coated on a plastic film to a thickness of about 95 μm with a solid content of 13 y/d using a metering bar coating method, dried at about 105°C for 5 minutes, and then heated at 70°C at 70°C.
A recording medium + CI was obtained by surface treatment using a heating and pressure calender of lf/(1).

Calcium carbonate powder 30% Silica powder 5% Polyvinylpyrrolidone 3% Octadecyl acetate 3% Pure water Remaining amount comparative example 1 Same as the recording medium (5) of Example 1 except that the aluminum chloride treatment was not performed (the recording medium I got the.

Comparative Example 2 A recording medium was obtained in the same manner as in Example 2 (Bl) except that the polyamine treatment was not performed.

Comparative Example 3 Using the same dispersion as in Example 3 (in Q, except for excluding octadecyl acetate), the recording medium (
Using the inks and recording media shown in Examples 1 to 3 and Comparative Examples 1 to 3, a nozzle diameter of 308 m was obtained.
Printing was performed by an inkjet recording method under conditions where the excitation frequency of one injection was approximately 100 KI (z), and an image sample was obtained.

Next, the following evaluation tests were performed on these image samples. The results are shown in Table-1.

(1) Evaluation of image water resistance: The image was immersed in water Ic at 30° C. for 1 minute, and the amount of change in image density before and after immersion was evaluated as the density fading rate.

(2) Evaluation of image light fastness The image was irradiated with a carbon arc lamp for 5 hours, and the fading rate of color reflection density at that time was evaluated. (Fading rate is the same as (2)) Table 1 Effects From the above table, it is clear that images printed by the inkjet recording method of the present invention have good light resistance and especially water resistance due to the combination of specific ink and recording medium. It is clear that it will be excellent.

Furthermore, the images obtained by the inkjet recording method of the present invention are excellent in other properties as well. For example, in terms of color tone, it is possible to obtain a color tone that is not found in conventional yellow, but this is due to the specific structural formula used. All of the dyes expressed have a spectral spectrum close to the ideal color (400 to 5 Q
This is also thought to be due to the fact that the absorption at Q nm is large (reflection at 500 nm to 700 nm is large).

Furthermore, the ink has excellent jetting properties and storage stability.

Patent applicant Ricoh Co., Ltd.

Claims (2)

[Claims] (1) Use of an ink containing a heptanoazopyrazolone dye and a recording medium containing at least one of water-soluble metal salts of divalent or higher valence metals, polyamines, alkylamine salts, and quaternary ammonium salts. Characteristic inkjet recording method. (2) The inkjet recording method according to claim (1), wherein the mono-azo-pyrazolone dye is represented by the following general formula. or -+-+ R2: alkyl group, -Coo M, -80,1vl-
10R3: hydrogen atom, alkyl group, -803M, hydroxyl group, -coa'M, halogen group m, n: any integer of 0, 1, 2.3 M: alkali metal, amine cation, ammonium For ions −+ R1-R11, the sum of S OB M and 1000 M is at least 2 fA.