JPH0448637B2 - - Google Patents

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 magenta ink. Prior Art In recent years, in the field of inkjet recording technology, technological development for reproducing color images has been actively conducted, and various research has 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 magenta ink that satisfies all three characteristics of color tone, water resistance, and light resistance has not yet been obtained. For example, images obtained using inks containing the dyes CI Acid 52 or CI Acid 227, which are known as magenta, have poor tone and lightfastness, and also have poor color tone and light fastness.
Inks containing I. Acid 94 have drawbacks such as poor light resistance and water resistance. Conventionally, in order to solve these shortcomings, various efforts have been made to improve the color tone through color correction, as well as the composition of the ink, especially the selection of dyes, and the recording medium, but none of these efforts have been fully satisfactory. The current situation is that we have not achieved the desired results. Purpose The present invention is aimed at solving the above-mentioned drawbacks, namely, in the field of inkjet recording technology, it is an object of the present invention to provide a method for reproducing magenta color images with a sufficiently satisfactory tone and having excellent light fastness and water fastness. The object of the present invention is to provide an inkjet recording method. Structure The present inventors have discovered that, as a means to solve the above-mentioned drawbacks, a combination of an ink containing a dye represented by a specific structural formula and a recording medium treated with a specific material is sufficiently effective. We have arrived at the present invention. That is, the inkjet recording method of the present invention contains an ink containing a dye represented by the following general formula and at least one of a water-soluble metal salt of a divalent or higher valent metal, a polyamine, an alkylamine salt, and a quaternary ammonium salt. It is characterized by using a recording medium. R ₁ and R ₂ are represented by the following general formula. X; O, S, SO ₂ M; H, Li, Na, K, amine or ammonium P; 1 or 2 m, n; an integer of 0 to 3 R ₃ ; hydrogen, alkyl (C is 1 to 5), amino ,
Hydroxyl group or halogen In addition to the dye and water described above, 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 0.5 to 30% by weight, preferably 1.5 to 6% by weight, based on the ink. Specific examples of the dye are listed below. Examples of wetting agents include polyhydric alcohols and alkyl ethers of polyhydric alcohols, which can be used in an amount of 5 to 30% by weight based on the ink. A specific example is shown below. <Polyhydric alcohol> Ethylene glycol, diethylene glycol,
Triethylene glycol, propylene glycol, glycerin, polyethylene glycol (20~
500), 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, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether etc. In the recording method of the present invention, among these wetting agents, a mixture of glycerin and diethylene glycol is preferable, as it has stable performance even after the ink is left for a long period of time.
Particularly preferred are those containing 1/1 to 1/5 diethylene glycol. In the present invention, the above-mentioned other wetting agent may be further added to the mixture. 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; N
-Methyl-2-pyrrolidone, 2-pyrrolidone 1.3
- Nitrogen-containing polycyclic compounds such as diethylimidazolidinone; intramolecular ester compounds of oxycarboxylic acids such as valerolactone caprolactone; carsolve acetate compounds such as ethylene glycol monomethyl ether acetate The recording method of the present invention has been described above. By combining this ink with the following specific recording media, the desired purpose can be achieved. 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, and more specifically, on a substrate, ( There are 1) types in which a coating layer containing such a treatment agent is provided, and (2) types in which a treatment agent is impregnated into the substrate without providing a particular coating layer. Regardless of the type of processing agent, better results can be obtained if the content of the processing agent is slightly larger in case (1) than in case (2). In the present invention, at least 0.2 g/m 2 , preferably 1.0 g/m ² or more of water-soluble metal salts of divalent or higher metals are added.
It is contained at a ratio of g/m ² or more. Specific examples of the metal salts are shown below. (Divalent metal salt) MgCl ₂ , CaBr ₂ , Ca(NO ₃ ) ₂ ,
CaI ₂ , ZnCl ₂ , ZnBr ₂ , ZnI ₂ , Zn(ClO ₃ ) ₂ ,
ZnSO ₄ , Zn(NO ₃ ) ₂ , SrI ₂ , SrBr ₂ , SrCl ₂ ,
Sr( _NO3 ) ₂ , _BaCl2 , Ba( _NO3 ) ₂ , Ba(OH)
₂ , _BaI2 , _BaBr2 , Fe( _NO3 ) ₂ , Ni( _NO3 ) ₂
Ni(SO ₄ ), NiCl ₂ , CUCl ₂ , CuSO ₄ (trivalent metal salt) AlCl ₃ , Al ₂ (SO ₄ ) ₃ , Al(NO ₃ ) ₂ ,
ScCl ₃ , Sc (NO ₃ ), Sc ₂ (SO ₄ ) ₃ , Ga (NO ₃ )
₃ , GaCl ₃ , Ga ₂ (SO ₄ ) ₃ , InCl ₃ , Fe(NO ₃ )
_3. Various alum (tetravalent metal salts) TiCl ₄ , GeCl ₄ , Zr(SO ₄ ) ₂ ,
SnCl ₄ , Sn(SO ₄ ) ₂ , Pb(CH ₃ COO) ₂ Among these specific examples, AlCl ₃ , Al(SO ₄ ) ₃ , Al(NO ₃ ) ₃ , ZnCl ₂ ,
Particularly preferred are ZNSO ₄ , SnCl ₄ , CaCl ₂ , MgCl ₂ and InCl ₃ . Alkylamine salts should be 0.05g/ ^m2 or more, especially
It is preferable to contain 0.2 g/m ² or more. 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, eicodecylamine acetate, or ^{hydrochloride} of the above alkylamine.
It is preferable to contain m ² or more. A specific example is shown below. The quaternary ammonium salt such as polyamide polyamine, polyoxyethylene alkylamine polyethylamine-epichlorohydrin, polydimethylaminoethyl methacrylate or polyalkylammonium is preferably contained in an amount of 0.1 g/m ² or more. A specific example is shown below. Lauryltrimethylammonium bromide or chloride, cetyltrimethylammonium bromide or chloride, octaisoquinolium bromide or chloride, hexadecyltrimethylammonium bromide or chloride, etc. Recording media in which the substrate is directly impregnated with the above 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 the substrate is prepared by dipping or coating the solution or dispersion of the processing agent. Next, a structure in which a coating layer is provided on a substrate will be described below. As the substrate, for example, cellulose-based paper, synthetic paper, plastic film, glass, metal plate, or metal foil can be used, regardless of its ability to absorb ink liquid. 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. A Resin-based oxidized starch, etherified starch, esterified starch,
One or more of dextrin, casein, gelatin, gum arabic, vegetable protein cellulose, carboxymethylcellulose, hydroxyethylcellulose, cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone, maleic anhydride resin, vinyl acetate polymer, polyvinyl butyral, polyacrylamide, etc. mixtures, copolymers and modified polymers of the above polymers, etc. B Latex type Polyvinyl acetate polymer latex, styrene
modified products such as isoprene copolymer latex, styrene-butadiene copolymer latex, acrylic polymer latex, acrylic-vinyl acetate copolymer latex, methyl methacrylate-butadiene copolymer latex and copolymers; As pigments such as mixtures, the following can be listed. 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; calcium carbonate, magnesium carbonate, barium sulfate, tisane white, etc. are preferred from the viewpoint of whiteness, dispersibility, and stability of the substance. Various methods can be considered for forming the coating layer of the recording medium, including (1) forming a layer consisting of a binder and additives, applying a processing agent, and then drying; 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. By methods such as coating method, reverse roller coating method, etc.
It is applied to a substrate and dried by hot air or heating to give a coating amount of 0.1 g/m ² to 60 g/m ² , preferably 3 g/m 2 .
Apply a layer of 20g/ ^m2 to 20g/ ^m2 , then apply 0.1wt of treatment agent.
% to 30 wt % is applied using one of the coating methods for layer formation described above, and dried to obtain a recording medium used in the present invention. Further, the recording medium obtained by the method (1) or (2) above is heated to a temperature of, for example, 50°C to 200°C, preferably
The properties of the recording medium can be improved by performing calendering under the conditions of 60° C. to 120° C. and a pressure of 10 Kg/cm to 150 Kg/cm, preferably 50 Kg/cm to 80 Kg/cm. Next, the present invention will be explained with reference to examples. Here, all percentages represent weight percentages. Example 1 A mixture having the following composition was heated and stirred at 70° C. for 3 hours to dissolve, and the mixture was passed twice through a membrane filter with an opening diameter of 0.45 μm to prepare ink A. Dye of specific example (1) 3.0% Glycerin 5.5% Diethylene glycol 16.5% Sodium dehydroacetate 0.2% Sodium thiosulfate 0.01% Sodium ethylenediaminetetraacetate 0.01% Pure water Remaining amount After dispersing the following composition for 10 hours using a ball mill dispersion method. The dispersion was applied onto 80 μm thick high quality paper using a doctor blade method at a solid content of 13 g/m ² and dried at 120° C. for 5 minutes to form a surface coating layer. Calcium carbonate powder 36% Aluminum hydroxide powder 4% Styrene-butadiene copolymer latex (solid content) 18% Casein 5% Water Remaining amount Next, a 6% aqueous solution of aluminum chloride was applied using an air knife coating method, with a solid content coverage of 1.5 g/ ^m2 and dried at 110℃ for 10 minutes, then 65℃, 65Kg/m2.
Recording medium A was prepared by performing heat-pressure calendering of cm. Example 2 A mixture having the following composition was stirred at 70° C. for 3 hours to dissolve it, and then passed through a membrane filter with an opening size of 0.25 μm twice to prepare ink B. Dye of the above specific example (3) 4% Glycerin 4% Diethylene glycol 13% Deltop 33 (Takeda Pharmaceutical) 0.5% Pure water 65.5% On the other hand, a 2% aqueous solution of Sunfix 555 manufactured by Sanyo Chemical Co., Ltd. was added to M-coat inkjet paper manufactured by Mitsubishi Paper Mills. After coating with a wet coating weight of 25g/ ^m2 using the air knife coating method, it was dried at 105℃ for 12 minutes.
Recording medium B was obtained. Example 3 Ink C was prepared by stirring a mixture having the following composition at 70° C. for 3 hours to dissolve it, and then passing it twice through a membrane filter with an opening size of 0.25 μm. Dye of the above specific example (5) 6% Diethylene glycol 22% Glycerin 6% Triethanolamine 5% Hokuside LX-2 0.5% Pure water Remaining amount Next, apply 3wt of octadecylamine acetate to 95μm thick plain paper with a size degree of 1Sec. % aqueous solution was applied to obtain a recording medium C having a coating amount of the processing agent of 0.6 g/m ² . Comparative Example 1 In Example 2, an ink having the same composition as ink B except that the dye in ink B was changed to CI Andreed 92, and Mitsubishi Paper M coated inkjet paper was used as the recording medium. As described above, using each ink and recording medium shown in Examples 1 to 3 and Comparative Example 1, printing was performed by the inkjet recording method under the conditions that the nozzle diameter was 30 μm and the ejection excitation frequency was approximately 100 KHz, and image samples were obtained. Obtained. Next, for these image samples, see (1) ~
Evaluation test (3) was conducted. The results are shown in Table-1. (1) Color evaluation of printed area Hue error and grayness were evaluated using the GATF color evaluation method. (2) Image water resistance evaluation The image was immersed in water 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. Fading rate (%) = amount of change/initial value x 100 (3) Evaluation of image light resistance A carbon arc lamp was irradiated for 4 hours, and the fading rate of color reflection density at that time was evaluated. (Fading rate is the same as (2)

[Table] Effects From the table above, it can be seen that images printed by the inkjet recording method of the present invention can be superior in color tone, water resistance, and light resistance by combining specific inks and recording media. it is obvious. Incidentally, the ink and the recording medium themselves are also excellent in terms of properties such as storage stability and mechanical strength.

Claims (1)

[Scope of Claims] 1. A recording medium containing an ink containing a dye represented by the following general formula and at least one of a water-soluble metal salt of a divalent or higher valent metal, a polyamine, an alkylamine salt, and a quaternary ammonium salt. An inkjet recording method characterized by using. R ₁ and R ₂ are expressed by the following formula; X; O, S, SO ₂ M; H, Li, Na, K, amine or ammonium P; 1 or 2 m, n; an integer of 0 to 3 R ₃ ; hydrogen, alkyl (C is 1 to 5), amino ,
Hydroxyl or halogen