JP3440542B2 - Recording liquid - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a black recording liquid. In particular, the present invention relates to a black recording liquid suitable for inkjet recording. [0002] Conventionally, as a recording liquid for ink jet recording, an aqueous ink in which an acid dye or a direct dye is dissolved in an aqueous medium, or a solvent-based ink in which an oil-soluble dye is dissolved in an organic solvent has been used. Have been. Since the solvent-based ink uses a solvent, it has a problem in terms of environmental safety, has a limited use, and cannot be used in an office or the like. On the other hand, since the water-based ink uses a water-soluble dye, there is a problem that the recorded matter has poor water resistance especially when recorded on plain paper. [0003] In order to improve the water resistance of aqueous inks, carbon black is used as a coloring material, and an aqueous dispersion ink in which carbon black is dispersed in an aqueous medium is used in part. However, this aqueous dispersion ink of carbon black has a problem that the recording density of the recorded matter is lower than that of the dye-based ink. In order to improve the recording density, it has been studied to add water-soluble phthalocyanine dyes, direct dyes, basic dyes, various water-soluble azo dyes, and the like to carbon black as dyes (JP-A-3-66768, JP-A-3-140377, JP-A-4-332773,
JP-A-2-276872, JP-A-2-276873
JP-A-2-276875, JP-A-4-57859
JP-A-4-57860, JP-A-4-57861
JP-A-4-57862, JP-A-4-57863
JP-A-4-57864, JP-A-4-57865
No., JP-A-4-59879, etc.). But,
In these improved methods, a water-soluble dye is used, so that a completely water-resistant recorded matter cannot be obtained. SUMMARY OF THE INVENTION The present invention has good water resistance and enables high-density recording even when recorded on plain paper for ink jet recording. Provides a black recording liquid that has excellent printability, good recording quality, color tone, light fastness other than water resistance such as light resistance, and good stability when stored for a long time. It is intended to do so. The gist of the present invention is to provide an aqueous medium, a dispersant, carbon black and 500 to 700 nm.
Wherein the recording liquid contains a non-water-soluble dye other than a phthalocyanine dye having an absorption maximum in the range of Hereinafter, the present invention will be described in detail. As the dye used in the recording liquid of the present invention, any dye may be used as long as it is a water-insoluble dye having an absorption maximum in the range of 500 to 700 nm, that is, a dye having substantially no solubility in water. Although good, there can be used those which are commercially available as red, purple, blue, green, and black disperse dyes, oil-soluble dyes, solvent dyes, resin coloring dyes, pigments, and the like. Specifically, Disperse Red, Disperse Violet, Disperse Blue, Disperse Green, Disperse Black, Solvent Red, listed in the color index,
Solvent Violet, Solvent Blue, Solvent Green, Solvent Black, Pigment Red,
Pigments such as CI Pigment Violet, Pigment Blue, and Pigment Black can be used, but other than these, dyes such as azo-based, anthraquinone-based, azomethine-based, and fused ring-based can also be used. As the carbon black used in the recording liquid of the present invention, commercially available carbon black can be used. The carbon black has a particle diameter of 10 to 100 nm, a DBP oil absorption of 40 to 180 ml / 100 g, and a pH of 40 to 180 ml / 100 g. Those having 2 to 10, especially 3 to 9, are preferred. As specific examples, for example, products # 10, # 30, # 39, and # 4 manufactured by Mitsubishi Kasei Co., Ltd.
0, # 42, # 45, # 48, # 52, # 95, # 26
00, MA7, MA8, MA11, MA100, MA2
30, MA600, and the like. Examples of the dispersant used in the recording liquid of the present invention include various anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, polymer-based dispersants, and the like. Is mentioned. Examples of the anionic surfactant include fatty acid salts, alkyl sulfate salts, alkyl benzene sulfonates, alkyl naphthalene sulfonates, sulfosuccinates, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates, alkyl phosphates, and polyoxyethylene. Alkyl sulfates, polyoxyethylene alkyl allyl sulfates, alkane sulfonates, naphthalene sulfonic acid formalin condensates, polyoxyethylene alkyl phosphates, α-olefin sulfonates and the like. As nonionic surfactants, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene derivatives,
Oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, etc. No. Examples of the cationic surfactant and the amphoteric surfactant include alkylamine salts, quaternary ammonium salts, alkylbetaines,
Aminooxides. Examples of the polymer dispersant include polyacrylic acid, styrene / acrylic acid copolymer, styrene / acrylic acid / acrylic acid ester copolymer, and styrene / (anhydrous) maleic acid copolymer ((anhydrous)
Maleic acid means maleic anhydride or maleic acid), styrene / (anhydride) maleic acid / acrylate copolymer, styrene / methacrylic acid copolymer, styrene / methacrylic acid / acrylate copolymer, styrene / Maleic acid half ester copolymer, vinyl naphthalene / (anhydrous) maleic acid copolymer, vinyl naphthalene / acrylic acid copolymer or salts thereof. Among these, anionic surfactants, nonionic surfactants and polymer dispersants are particularly excellent. The aqueous medium used in the recording liquid of the present invention is mainly composed of water, but it is preferable to use a water-soluble organic solvent added to water. Examples of the water-soluble organic solvent include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol (# 200, # 400), glycerin, alkyl ethers of the above glycols, N-methylpyrrolidone, 1,3- Dimethyl imidazolinone, thiodiglycol, 2-pyrrolidone, sulfolane, dimethyl sulfoxide, diethanolamine, triethanolamine, ethanol, isopropanol and the like. [0010] In addition to the above components, a water-soluble resin, a fungicide, a bactericide, a pH adjuster, urea, and the like may be added to the recording liquid of the present invention as needed. The method for preparing the recording liquid of the present invention is carried out by mixing the above-mentioned components, grinding the aggregated particles of the carbon black and the dye into fine particles using a disperser, and subjecting them to a dispersion treatment. Ball mill as dispersing machine,
Roll mill, sand grind mill, etc. are used,
Particularly, a sand grind mill is preferable. After grinding and dispersion, coarse particles are removed using a filter or a centrifuge. The particle size of the aggregated particles of carbon black and dye is 1
It is desirable to adjust it to not more than μm. Components other than carbon black, a dye, a dispersant, and water may be added after grinding and dispersion treatment. In addition, since the grinding and dispersion treatment can be efficiently performed by performing the treatment at a high concentration, it is preferable that the treatment liquid prepared at a high concentration is finally diluted with an aqueous medium to adjust the concentration of the recording liquid. Carbon black is used in an amount of 1 to 10 with respect to the recording liquid.
It is preferably used in the range of weight%, but 3 to 8 weight% is particularly preferable. The dye is 10 to carbon black.
It is preferably used in the range of 100% by weight,
0% by weight is particularly preferred. The dispersant is preferably used in the range of 5 to 100% by weight based on the total amount of the carbon black and the dye, and particularly preferably 20 to 50% by weight. The amount of the water-soluble organic solvent used in the recording liquid is preferably in the range of 5 to 30% by weight, particularly preferably 10 to 20% by weight. One type of these carbon blacks, dyes, dispersants and organic solvents may be used alone, but in some cases two or more types may be used in combination to further enhance the effect. According to the recording method of the present invention using the recording liquid of the present invention, it is possible to perform recording with good dischargeability and high reliability, and it has good water resistance even when recording on plain paper. Further, it is possible to obtain a black recorded matter having a higher recording density and good fastness other than water resistance such as print quality, color tone and light fastness. Since the present invention has the above-mentioned characteristics, it can be used as a recording liquid for other applications without being limited to ink jet. Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples unless it exceeds the gist thereof. Example 1 (Preparation of recording liquid) [Table 1] Composition of recording liquid Amount used (parts) Glycerin 34 Lipolan PB-800 (Lion Corporation product) 11 Carbon black # 45 (Mitsubishi Kasei Corporation product) 11) Dye 2 in Table 2 (A) below 2 Deionized water 42 Total 100 Lipolan PB-800 is an α-olefin sulfonic acid-based dispersant. Each of the above components was placed in a stainless steel container and pulverized for 60 hours using a sand grinder together with 152 parts of glass beads having an average diameter of 0.5 mm.
After diluting and stirring the obtained liquid with 127 parts of ion-exchanged water, Pressure filtration was performed using a 5C filter paper, and the filtrate was used as a recording liquid. (Printing Test) An ink-jet printer (DeskJet) was prepared by using the recording liquid obtained in the above embodiment.
Electrophotographic paper (Xerox 4024 paper, Xer) using 1200C, product of Hewlett-Packard Company
As a result of performing ink-jet recording on OX Corporation product), a stable and good ejection property without clogging or the like was exhibited, and a printed matter having good print quality was obtained. (Evaluation of Print Density) The density of the printed matter obtained in the above print test was measured using a Macbeth reflection densitometer (RD914). The evaluation results are shown in Table 1 below. (Water Resistance Test) The printed matter obtained in the printing test was immersed in tap water taken in a beaker for 5 seconds or 5 minutes. 5
In the second water immersion test, after the printed matter was dried, the presence or absence of character stain was visually determined. The results were classified as follows. ２: almost no character dirt △: slight character dirt but no problem in practical use x: severe character dirt Macbeth reflection after drying printed matter for 5 minutes immersion test The print density was measured using a densitometer (RD914), and the ratio of the optical density after immersion to the optical density before immersion was expressed as a percentage as a residual ratio. In this evaluation method, the larger the number, the better the water resistance. The results are shown in Table 1 below for both the 5-second immersion test and the 5-minute immersion test. (Light fastness test) The printed matter was irradiated with a xenon fade meter (manufactured by Suga Test Instruments Co., Ltd.) for 100 hours to visually evaluate the discoloration and discoloration. The results were classified as follows and are shown in Table 1 below.表: good…: discolored and discolored, but no problem in practical use x: severely discolored and discolored (Storage stability test of recording liquid) The recording liquid was sealed in a Teflon container, Stored at ℃ for one month. The presence or absence of gelation or precipitate was visually evaluated. The results were classified as follows and are shown in Table 1 below. ４: Almost no gelation or precipitate 沈: Slightly gelation or precipitate observed, but no problem in practical use ×: Severe gelation or precipitate 2 to 14 Example 1 except that the dyes (B) to (N) shown in Table 2 were used instead of the dye (A) used in Example 1.
Preparation of recording liquid, printing test, evaluation of print density, water resistance test, light resistance test, and storage stability test of recording liquid were carried out in the same manner as described above, and the results shown in Table 1 were obtained. Example 15 In the same manner as in Example 1 except that the dyes (M) and (L) shown in Table 2 were partially used instead of the dye (A) used in Example 1, respectively. Preparation of the recording liquid, printing test, evaluation of print density, water resistance test, light resistance test, and storage stability test of the recording liquid were performed, and the results shown in Table 1 were obtained. Example 16 The procedure of Example 1 was repeated except that the dyes (M), (L) and (J) shown in Table 2 were partially used instead of the dye (A) used in Example 1. Preparation of a recording liquid, printing test, evaluation of print density, water resistance test, light resistance test, and storage stability test of the recording liquid were performed in the same manner, and the results shown in Table 1 were obtained. Example 17 Preparation of a recording liquid and printing test in the same manner as in Example 1 except that carbon black MA230 (manufactured by Mitsubishi Kasei Co., Ltd.) was used instead of carbon black # 45 used in Example 1. A print density evaluation, a water resistance test, a light resistance test, and a storage stability test of the recording liquid were performed, and the results shown in Table 1 were obtained. Comparative Example 1 (Preparation of recording solution) 11) Ion-exchanged water 44 ───────────────────────────────── Total 100 Recorded in Example 1 A recording liquid was prepared in the same manner as in Example 1 except that the composition of the liquid was as described above. A printing test, a water resistance test, a light resistance test, a storage stability test, and evaluation using the recording liquid were performed in the same manner as in Example 1. The evaluation results are shown in Table 1 below. Comparative Example 2 (Preparation of recording liquid) [Table 6] Composition of recording liquid Used amount (part) Glycerin 34 Lipolan PB-800 (Lion Corporation product) 11 Carbon black # 45 (Mitsubishi Kasei Corporation product) ) 18 ion-exchanged water 37 ───────────────────────────────── total 100 Recorded in Example 1 A recording liquid was prepared in the same manner as in Example 1 except that the composition of the liquid was as described above. Using this recording liquid, a printing test, a water resistance test, a light resistance test, a storage stability test, and evaluation thereof were performed in the same manner as in Example 1. The evaluation results are shown in Table 1 below. Comparative Example 3 (Preparation of recording liquid) Composition of recording liquid Used amount (parts) Glycerin 34 Lipolan PB-800 (Lion Corporation product) 11 Carbon black # 45 (Mitsubishi Kasei Corporation product) 11) Food Black 22 Ion-exchanged water 42 ───────────────────────────────── Total 100 1, a recording liquid was prepared in the same manner as in Example 1 except that the composition of the recording liquid was as described above. Using this recording liquid, a printing test, a water resistance test, a light resistance test, a storage stability test, and evaluation thereof were performed in the same manner as in Example 1. The evaluation results are shown in Table 1 below. [Table 8] [Table 9] [Table 10] [Table 11]

Continuation of the front page (56) References JP-A-7-268258 (JP, A) JP-A-3-66768 (JP, A) JP-A 64-36667 (JP, A) JP-A 64-74277 (JP) , A) JP-A-64-180 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C09D 11/00-11/20

Claims (1)

(57) [Claims] 1. An aqueous medium, a dispersant, and a DBP oil absorption of 40.
~ 180ml / 100g carbon black , and 50
It has an absorption maximum in the range of 0 to 700 nm, is insoluble in water, and contains a dye other than a phthalocyanine-based dye ,
A carbon black concentration of 1 to 10% by weight,
The amount of non-Russianine pigment is 10% of carbon black.
A recording liquid characterized by being in the range of 100 to 100% by weight .