JPS59133273A - Ink jet recording method - Google Patents

Abstract

PURPOSE:To obtain a printed image having good color tone and excellent resistance to water and light, by combining a recording medium contg. a bivalent or polyvalent water-soluble metal salt with an ink jet recording soln. contg. a specified dye. CONSTITUTION:A wetting agent (e.g. a solvent mixture of glycerol and diethylene glycol in a ratio of 1/1-1/5), an antiseptic, a dye of the formula (wherein M is Li, Na, K), etc. are dissolved in water to obtain an ink jet recording soln. A support is coated with a dispersion mainly composed of a pigment (e.g. talc) and a binder (e.g. PVA) and dried to provide a recording layer in a coating amount of 0.1-60g/m<2> thereon. The recording layer is then coated with an aq. soln. of 0.1-30wt% at least one member selected from bivalent or polyvalent water-soluble salts, polyamine derivatives, alkylamine salts and quaternary ammonium salts and dried to obtain a recording medium. Jet recording is conducted on this recording medium by using the above recording soln.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to an inkjet recording method comprising a combination of a recording medium containing a water-soluble metal salt having an ionic valence of two or more and a specific inkjet recording liquid.

BACKGROUND ART Conventionally, magenta ink with a good tone (ideal magenta color) has not existed, so it is necessary to select one from among those with a tone close to magenta. Further, in order to obtain an image with good color reproduction tone balance, a color correction means is required. Furthermore, since magenta dyes have a unique spectral reflection spectrum, their color fades more easily when exposed to light (, Y
Among the three colors of MO, fading is the most remarkable.

Even in a colored image, only the color in the magenta portion is erased or the density is greatly reduced, resulting in the problem of poor color balance. In addition, magenta ink is one of the factors that deteriorates color reproduction.
This is thought to be because the dye must have sufficient reflection in two separate reflection zones, which requires very difficult properties in terms of the structural properties of the dye. In general, a band spectrum with two peaks has a reddish and bluish tinge because the size and contour of each peak are not good, and it is very difficult to balance the two reflection spectra. . Furthermore, since dyes with a good color tone close to magenta have a strained skeleton structure, they tend to undergo reverse structural destruction and mutation due to external factors such as light irradiation, and tend to fade more rapidly than other dyes.

Purpose The present invention has been made in view of the above problems, and the purpose of the present invention is to provide a magenta color image with good color tone and high ink ejection reliability, and to be particularly effective in water resistance processing of images and to improve light resistance. The purpose of the present invention is to provide a complete inkjet recording method that realizes excellent inkjet printing.

Structure In order to achieve the above object, the present invention is constructed by combining a recording medium rich in a specific substance and an inkjet recording liquid containing a specific dye. That is, the inkjet recording method of the present invention uses a recording medium containing on its surface at least one of a water-bathable metal salt, a polyamine condensate, an alkylamine salt, or a quaternary ammonium salt containing an ion valence of two or more. , at least one of the ink colorants has a structural formula (wherein M is Na or M
The method is characterized in that an inkjet recording liquid containing a dye having the following properties is applied.

Examples of dyes having the above structural formula include C and I.

Acid Red 289 magenta dye can be used. This dye is one of the closest to the ideal color of magenta compared to many magenta dyes, and has excellent color tone as a coloring material for inkjet magenta ink aimed at full color reproduction. It shows stable physical properties.

This dye has good light resistance, which is important for full-color dyes, and full-color printed images are generally displayed in places that are always exposed to external light, such as on walls. Therefore, fading due to light is the biggest problem. In this respect, this dye is very excellent even if it is VCL-.

The characteristics of the dye used in the present invention are shown below.

1) The dye used in the present invention exhibits a color tone close to the ideal magenta color, which is excellent as a magenta dye.

GATF color evaluation value, hue error 45° or less, grayness 6
5 or less.

2) The dye used in the present invention exhibits excellent solubility in polyhydric alcohol (wetting agent of the ink component) and water (main component of the ink component). This will give you the ability to spray ink.

The dye used in the present invention has excellent light resistance (under carbon arc lamp) despite being a xanthine dye. 6-hour irradiation fading rate (within 5%), and also on recording media containing all ions (IIIJ@ divalent or higher water-bathable metal salts, maytvbovrmine condensates, alkylamine salts, or quaternary ammonium salts). Water resistance (fading rate after 1 minute immersion in 60°C warm water is 6)
%) also exhibits very excellent properties.

The inkjet recording liquid used in the present invention contains, in addition to the dye having the above structural formula, water, a wetting agent, and an antiseptic and antifungal agent. and a viscosity modifier, etc., may all be blended.

Wetting agent is glycerin/diethylene glycol = 1/1~
Preferably, the di-inkjet recording liquid has good jetting stability and jetting response, but the jetting response and reliability are particularly poor after being left for a long period of time. Is this ha? lJ Eva C, 1, Acid Red 2
89 dye (inorganic salt 50 ppm or less, purity 99.8%)
This is because it has better bath solubility than wetting agents (glycerin/diethylene glycol type). For example, for a solvent of glycerin/diethylene glycol=1/6, it is 21% by weight at room temperature of 20°C, which is very good.

Further, in order to adjust the physical properties of the ink to desired values, the following polyhydric alcohols and alkyl ethers of polyhydric alcohols can be added in an amount of at least 40% by weight based on the total amount of the wetting agent.

Examples of polyhydric alcohols include ethylene glycol, triethylene glycol, fluoropylene glycol, polyethylene glycol (20 to 500), and polypropylene glycol. Alkyl ethers of polyhydric alcohols: ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl There is ether etc.

Other additives include amines such as triethanolamine, N-methyl-2-pyrrolidone, 2-pyrrolidone,
Examples include nitrogen-containing polycyclic ring systems such as 1,6-dimethylimidazolidinone, intramolecular ester systems of oxycarboxylic acids such as valerolactone and caprolactone, and cell solve acetate systems such as ethylene glycol monomethyl ether acetate-1. 1, for example C, 1, Acid Red 289
In, Rinaka (7) fj'i cup・Has 0.5 weight 1A-
X -30% by weight, preferably 1.5% to 6% by weight, is optimal.

Next, the recording medium used in the present invention will be explained. In the present invention, a waterproofing agent is contained in the recording medium in order to increase the waterfastness of the image.This method includes the following method.

This is a method of imparting water resistance to a recording medium by incorporating a water resistance treatment agent into the recording medium.
Seed gt Kame Ru. One method is to immerse or coat a recording medium with a processing agent solution and then perform treatment with a processing agent. Another method is to prepare a recording medium having an image-retaining coat layer containing a processing agent by coating a coating layer forming liquid containing a processing agent on a support.

Water resistance treatment agents include water-bathable metal salts containing divalent or higher ionic valences, bo-17 amine condensates, and alkyl-based metal salts.

Water-bathable metal salts preferably have a valency of 2 ([1h or higher). Specific examples include the following.

Divalent Mg072% OaBr2, OaOt2
, Oa(NO3)2 , Oatech2, ZnCl2, ZnB
r2, ZnIz, Zn(OtOg)2, ZnSO
4, Zn(NO5)2% Sr 2, SrBr2
, SrOA2% 13r(NO3)2, BaC! t2
, Ba(NO3)2 % Ba(○King)2
, Ba engineering 2, Baj31-2, Fs(N
O3) 2, 7(i()J C3)2, Ni(
504), NIC12, CuOA2.0uSO4,
Trivalent At0t3, At2(SO4)3, AA(N
C)3)3.5COt3,Sc(NO3)3.5C2(
304)! , % Ga(NO3)3, Gact3,
Ga2(Sc4)3, nct5, re(NOg)3
%Various Alumban 4 @il TiCt4, Ge0t4
, Zr(804)2, SnO',4,
5n(SO4)2p'b(cH3aoo)2゜Of the above, AtC171%AA2(SO4)3, AA
(NO3)3, ZnO12, Zn5Q4.5nOt4
% 0aCA2 s MgOA2, engineering n013 is particularly preferred.

Mixtures of several types of the above-mentioned processing agents may also be used, and these were excellent in each of the following items: whiteness, anti-fog properties, water resistance, color change, and light resistance. The content i of these processing agents in the recording medium is 0.297 m2 or more, particularly preferably 1.0'77 m2 or more.

Examples of the alkylamine end include decylamine acetate, unde-zylamine lactate, dodecylamine m-acid, lysodylamine acetate, tetradecylamine butyrate, R-ntadecylamine vinegar, and hexadecylamine Decylamine acetate, heptadecylamine acetate, octadecylamine acetate, nonadecylamine 1? i' acid salt, eicobucylamine acid salt, or the hydrochloride salt of the above-mentioned alkylamine. The amount of these processing agents applied to the medium is 0.05? /m2 or more, preferably 0.297m2 or more. moreover,
Quaternary ammonium salts include lauryltrimethylammonium bromide or chloride, cetyltrimethylammonium bromide or chloride, octaine chiturium bromide or chloride, hekylidecyltrimethylammonium bromide or chloride, and the content in the recording medium is 0.117'/m2. The above is preferable.

In addition, polyamine condensates include polyamide polyamine, polyoxyethylene alkylamine polyetheramine-ebichlorohydrin, polydimethylaminoethyl methacrylate, polyalkylammonium, etc., and the content in the recording medium should be 0.0597 m2 or more. preferable.

Next 1! A method for producing a single-layer recording medium includes, for example, using plain paper as a support with a size of 2 OS8C or less, a whiteness of 75% or more, a smoothness of 10 to 150, and a temperature of 6 to 120 sec, and a bath solution of the processing agent. Alternatively, there is a method of obtaining a recording medium by immersing it in a dispersion liquid or by immersing it in a dispersion liquid.
- The i-type recording medium is composed of a support, a depositing agent, and the like, and its main ingredients include a binder, a binder, a water improver, and a fine dispersing agent. Trace amounts of additives may also be used. Further, the support may be a member capable of absorbing ink liquid sufficiently or a member having no ability to absorb ink liquid, such as cellulose-based paper, synthetic paper, plastic film glass, metal plate, or foil.

As the binder for the surface recording layer of the recording medium in the present invention, the following may be mentioned.

A, resin-based oxidized bed powder, etherified starch, esterified starch textrin, casein, ceratin-arahya gum, M41i [
White cellulose, carboxymethylcellulose, hydroxyethylcellulose, cellulose derivatives, polyvinyl alcohol, polyvinylpyrrolidone, maleic anhydride resin, vinyl acetate polymer, polyvinyl butyral, polyacrylamide, etc., or a silk combination thereof, a copolymer of the above polymers. and modified polymers.

B, Latex polyvinyl acetate polymer latex, styrene-isoprene copolymer latex, styrene-butadiene copolymer latex, acrylic polymer latex, acrylic-vinyl acetate copolymer latex, methyl methacrylate.
Modified products such as butadiene copolymer latex and other copolymers, and mixtures of two or more layers.

Specific examples of pigments in the surface recording layer include the following.

Clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, magnesium carbonate, magnesium sulfate, barium sulfate, titanium oxide, zinc oxide, zinc oxide, zinc carbonate, titanium white, aluminum silicate, European silica, calcium silicate, oxide Aluminum, aluminum hydroxide silicate, aluminum hydroxide, zeolite. Among the above, calcium carbonate, magnesium carbonate, barium sulfate, and titanium white are preferred from the viewpoint of whiteness, dispersibility, and substance stability.

An example of a method for producing a recording medium according to the present invention will be described below. First, a dispersion containing a pigment and a binder as main components is applied to a support using a blade coating method, an air knife coating method, a roll coating method, a wire bar coating method, a spray coating method, a gravure coating method, or a reverse roller coating method. Apply by coating, dry with warm air or force O heat, and the coating amount after drying is 0.12
/m2~60g/m2 preferably 3? /m”～20?
A surface recording layer of /m2 is provided, and then an aqueous solution of a water resistance improver of o, 1*i:% to 30% by weight is applied on the surface recording layer type fi'j using one of the coating methods described above. It can be coated and dried to create a recording medium.

Furthermore, the recording medium produced as described above was heated at a heating temperature of 50° C. to 200° C., preferably 60° C. to 120° C., and a pressure of 40 kl IC'ln to 1
50 ky/m preferably 5 Q ky/cm ~
Calendaring at 80ky/cm results in an even more beautiful recording medium. Furthermore, when forming the surface recording layer, a recording medium may be prepared by dispersing pigments, binders, water resistance improvers, and other additives in the same manner, coating, drying, and calendering.

The present invention will be explained in more detail by the following examples together with comparative examples, but the present invention is not limited thereto. In the example,
Percentages are expressed by weight.

Example 1 Dye (sodium salt) 6.0% Glycerin 5.5% Diethylene glycol 16.5% Sodium dehydroacetate
0.2% Sodium Thiosulfate 0.0
1% ethylenediamine 4 ffl [sodium m
0.01% pure water
The remaining amount of the mixed vlJ was heated to 70° C., stirred and dissolved, and filtered twice through a membrane filter with a pore size of 0.45 μm to prepare an ink (Al).

Next, the above composition was dispersed in a ball mill dispersion method for -C for 10 hours.
The dispersion was added with a solid content of 16 by doctor blade method.
It was coated on 80 μm thick high-quality paper at t7m2 and dried at 120° C. for 5 minutes to form a surface record.

Next, a 6'A aqueous solution of conditioned aluminum was applied using the air knife coating method at a wet coating rate of 60 g/m2, dried at 110°C for 10 minutes, then dried at 65°C for 65ky.
The surface was smoothed using a heating and pressure calender of /α to obtain an inkjet recording medium.

Next, various evaluations of the ink and the recording medium were attempted by printing on this inkjet recording medium VC7il ink (Alk).

1) Image clarity and image drying property: Clear images were obtained when full ink jet recording was performed on commercially available high-quality paper using a nozzle with an inner diameter of 60 μm at a particle formation frequency of 100 KH2. The drying time of the recorded material was within 10 seconds at room temperature.02) Storage 4-42: Seal the ink in a glass container and store it at -20°C for 1 month.
It survived for 1 month at 20°C, 1 year at 20°C, and 1 week at 90°C, and no precipitation was observed. Also,
No change was observed in the physical properties or color tone of the ink.

6) Jetting stability: The jet recording described above in 1) was carried out continuously for 1000 hours, and stable recording was achieved without any clogging of the nozzle or change in the jetting direction.

4) Injection response: Jet control according to circle 1 ■convex 1)
1 month at normal temperature and humidity and 1 month at 40℃-60%RH
I left it alone for a week, and then performed the entire jet recording in 1) again, but I was able to make stable records just like in JJ 3).

5) Color evaluation of printed area: Hue error and grayness were fully evaluated using the GATF color evaluation method.

6) Surface recording and layer strength determination: Lead wheel surface hardness test (US method) 7) Image water resistance test: Subject to 60℃ flashing for 1 minute, and change in image density before and after immersion. 8) Image front light test: Irradiated with a carbon arc lamp for 6 hours, then Example 2 Dye (lithium) 4% Glycerin 10y6 diethylene glycol 20 g Pull Top 66 (Takeda Pharmaceutical) 0
．． 5% water 65.5X
The above compositions were mixed, heated to 70° C., and dissolved with stirring. Thereafter, the mixture was filtered twice using a membrane filter with an opening diameter of o and 25 μm to prepare an ink (Blf).

Next, a 29K water bath solution of Sunfix 555 (manufactured by Sanyo Chemical Co., Ltd.) was applied to M-coat inkjet paper manufactured by Mitsubishi Paper Mills by an air knife coating method to a wet coverage of 2597 m2, and dried at 105°C for 12 minutes. An inkjet recording medium was obtained.

An image sample was obtained by completely printing on the above recording medium using ink (El). Next, the ink and image nanoflu were evaluated in Example 1 and in batches. Comparative Example 1: Actual MIU2 ink (replaced with the same dye i0.K and Acid Red 92. Mitsubishi Paper M-coated inkjet paper was used as the recording medium. The ink and image were evaluated.

Example 6 Dye (sodium salt) 6% Diethylene glycol 12% Glycerin 4% Triethanolamine 5% Hokuzide LX-20.5% Silk water
The remaining amount or more was mixed, heated to 70°C, stirred and dissolved, and filtered twice through a membrane brush filter with a pore size of 0.45 μm to obtain an ink IC).
Bamboo.

Next, a 5% water bath solution of octadecylamine acetate was applied to plain paper with a thickness of 95 μm at a size degree of 1 sec, and 0.6 f.
A treatment agent adhesion amount of t/m2 was obtained. The above ink (C) was jet-printed onto this recording medium to obtain an image sample. Next, this ink and sample were evaluated in the same manner as in Example 1.

Effects According to the method of the present invention configured as described above, the color tone is good for magenta images, the reliability of ink varnish is high, and the effect is particularly large for water resistance processing of images, and light resistance is improved. It is possible to realize excellent inkjet printing.

Claims (1)

[Scope of Claims] An ink is applied to a recording medium containing on its surface at least one of a water-bathable metal salt having an ionic valence of two or more, a polyamine condensate, an alkylamine salt, or a quaternary ammonium salt. 1. An inkjet recording method characterized in that an inkjet recording liquid containing a dye in which at least one colorant has a structural formula (wherein M represents Li, Na, or K) is applied.