JP2001115070A - Ink jet printing liquid and method for ink jet printing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject liquid for ink jet printing use or for use in writing utensils, excellent in storage stability and issue stability, high in moisture retention, and causing no nozzle cloggings. SOLUTION: This ink jet printing liquid is obtained by incorporating an aqueous medium with pref. 2-15 wt.% of a coloring material (e.g. carbon black) and pref. 0.3-30 wt.% of xylitol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording liquid for an aqueous medium, and more particularly to a recording liquid for an ink jet or a writing instrument, and more particularly to a recording liquid suitable for an ink jet.

[0002]

2. Description of the Related Art Conventionally, as a recording liquid for ink jet recording, an aqueous ink in which an acidic 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. . Since the solvent-based ink uses a solvent, it has a problem in terms of environmental safety, and its use is limited because it is not suitable for use in offices and 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, particularly when recorded on plain paper.
Further, the recorded matter of the ink using these dyes is insufficient in light resistance. Such problems apply not only to ink jet inks but also to recording liquids for writing instruments.
In order to solve the above-mentioned problems, a pigment having excellent water resistance and light fastness is used as a coloring material, and an aqueous dispersion ink in which the pigment is dispersed in an aqueous medium is partially used. These pigment inks have been used mainly for outdoor exhibitions because of their excellent water resistance and light resistance.In recent years, however, recording liquids that use carbon black as a coloring material have excellent recording density, water resistance, and print quality. It is also rapidly spreading to applications used indoors, such as office printers and personal printers. However, a dispersed ink in which a coloring material insoluble in a solvent such as a pigment is dispersed has a problem that the dispersed particles in the ink are aggregated during long-term storage, and the nozzle is easily blocked when the printer is left unattended. Was a problem.

[0003]

SUMMARY OF THE INVENTION The present invention is excellent in storage stability and ejection stability for recording or writing implements of any type of ink jet (continuous type, on demand type, piezo type, thermal type, etc.). It is an object of the present invention to provide a recording liquid which has high property and does not cause clogging of nozzles, and which provides good fastness such as light resistance and water resistance of a recorded matter.

[0004]

Means for Solving the Problems The present inventors have proposed a recording liquid,
In particular, as a result of examining various recording liquids that are excellent in storage stability and ejection stability for ink jet and writing implements and that do not cause clogging of nozzles, the recording liquid characterized by containing xylitol is stored. The present invention has been found to provide a recording liquid which has excellent stability and ejection stability, has a high moisturizing property and does not cause clogging of nozzles, and has good light fastness of a recorded matter, and good fastness such as water resistance. It is. That is, the gist of the present invention resides in a recording liquid containing xylitol.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The recording liquid of the present inventors is characterized by containing xylitol. By adding xylitol, the storage stability of the recording liquid and the ejection stability can be improved as described above, and problems such as nozzle clogging can be solved.
This is probably because xylitol is excellent in moisturizing properties, so that such an effect can be exerted. The amount of xylitol used in the present invention is preferably 0.1 to 30% by weight based on the recording liquid in terms of storage stability, ejection stability, and prevention of nozzle clogging, and 1 to 20% by weight. Is more preferable, and 3 to 15% by weight is particularly preferable.

[0006] The recording liquid of the present invention can be preferably used as an ink to which a coloring material is added. On the other hand, color materials used for the purpose of imparting water resistance to the ink fixed on the recording material by mixing the ink with the recording material, or preventing bleeding at the boundaries between inks that are not the same color are used. It may be used as a performance imparting ink that does not contain it. As the coloring material used in the recording liquid of the present invention, any of a water-soluble dye and a water-insoluble dye can be used, and the types thereof include dyes (water-soluble dyes, disperse dyes, oil-soluble dyes) and pigments (organic dyes). Pigments, inorganic pigments) and any other types of coloring materials. As the coloring material of the present invention, known coloring materials used for ordinary recording liquids can be used, and specific examples of the coloring material are shown below, but are not limited by the following specific examples.

Examples of the water-soluble dye include an anionic dye including an acid dye, and a cationic dye. Specific examples include anthraquinone dyes, phthalocyanine dyes, indigoid dyes, xanthene dyes, triphenylmethane dyes, and azine dyes used in ordinary writing and ink jet recording liquids. Specific examples of such known dyes include C.I. I. Acid Yellow
w-9, 23, 69, C.I. I. Acid Red-3
3, 35, 37, 52, 289, C.I. I. AcidBl
ue-6, 9, 89, 174, C.I. I. Acid Bl
ack-1, 2, 16, 16, 17, 35, 41, C.I. I. D
direct Yellow-26, 86, 132, 14
2, C.I. I. Direct Red-3, 49, 10
1,227, C.I. I. Direct Blue-86,
199, C.I. I. Direct Black-17, 1
9,51,90,154,163,168,171,1
95, 200, C.I. I. Food Yellow-7,
C. I. Food Red-1, 3, 11, C.I. I. F
wood Black-1, 2 and the like, but are not limited thereto.

Examples of the water-insoluble dye include organic pigments, inorganic pigments, disperse dyes, oil-soluble dyes and the like, and specific examples include the following. Specific examples of the pigment used in the yellow ink include CI Pigment Yellow 1, 2,
3, 12, 13, 14, 16, 17, 73, 74, 75, 83, 93, 95, 9
7, 98, 114, 128, 129, 151, 154 and the like. Specific examples of the pigment used in the magenta ink include CI Pigment Red 5, 7, 12, 48 (Ca), 48 (M
n), 57 (Ca), 57: 1, 112, 123, 168, 184, 202 and the like. Specific examples of pigments used in cyan ink include CI Pigment Blue 1, 2, 3, 15: 3, 15: 3
4, 16, 22, 60, CI Bat Blue 4, 60 and the like. CI Pigment Red 209, 122, 224
, 177, 194, CI Pigment Orange 43, CI Bat Violet 3, CI Pigment Violet 19, 2
3, 37, CI Pigment Green 36, 7, CI Pigment Pro 15: 6, 209 and the like can also be used. Oil-soluble dyes include CI Solvent Yellow 16, 21, 25, 29, 33, 56, 8
2, 88, 89, 150, 151, 163, CI Solvent Red 2
4, 27, CI Solvent Blue 14, 25, 38, 48, 67, 6
8, 70, 132, CI Solvent Black 3, 5, 7, 2
7, 28, 29, 29, 34, etc. can be used.Other than that, Oil Yellow 105, 107, Varifast Yellow 1101, 1105,
Varifast Red 1306, Varifast Blue 1603, 16
07, 2610, Varifast Black 1802, 1807, 3830 (or more, manufactured by Orient Chemical Co., Ltd.), Aizen Spiron Yellow GRLH, 3RH, Aizen Spiron Blue GNH,
2BNH, BPNH, Aizen Spiron Black MH, GMH (or more,
Hodogaya Chemical Industry Co., Ltd.), Oleosol Blue G, Oleosol Plaque AR (all manufactured by Taoka Chemical Industry Co., Ltd.)
And Orasol Black RL1 (manufactured by Ciba Geigy). Examples of disperse dyes include CI Disperse Yellow 3, 82, 54, CI Disperse Red 60, 191 and CI Disperse Violet 57.

In the present invention, an excellent recording liquid can be obtained, particularly when carbon black is used as a coloring material.
Carbon blacks such as acetylene black, channel black (gas black) and furnace black can be used, but channel black (gas black) and furnace black are preferred, and furnace black is more preferred. The carbon black used has a DBP oil absorption of usually 60 to 1000 ml / 100 g, preferably 90 ml / 100 g or more, and 140 m / 100 g or more.
1/100 g or more, more preferably 140 ml / 100 g
g or more and 300 ml / 100 g or less are particularly preferable. The volatile matter of the carbon black is usually preferably 8% by weight or less, more preferably 4% by weight or less, particularly preferably 3% by weight or less. Further, BET specific surface area of the carbon black is preferably at least 150m ² / g, more preferably those of ^{200m 2 / g~1000m 2 / g,} 230m 2 / g~400m 2 / g is particularly preferred. The primary particle size is preferably 40 nm or less, more preferably 20 nm or less, and particularly preferably 16 nm or less in terms of storage stability, printing density and ejection stability of the recording liquid. Further, the pH of the carbon black is preferably 2 to 10, and particularly preferably 6 to 9.

The carbon black DBP referred to here
The oil absorption is a value measured by JIS K6221A method, the volatile content is a value measured by JIS K6221 method, and the primary particle diameter is an arithmetic mean diameter by an electron microscope. As the carbon black, any material having the above-mentioned physical properties can be used without particular limitation. As commercially available carbon black, # 2600, # 2300, # 990, # 980, # 960,
# 950, # 900, # 850, # 750, # 650, MCF-88, MA-600, # 95
, # 55, # 52, # 47, # 45, # 45L, # 44, # 40, # 33
, # 32, # 30, # 25, # 20, # 10, # 5 (Mitsubishi Chemical), Color Black FW1, FW2, FW2V, FW18, FW200
, Special Black 4, 4A, 5, 6, 100, 250, 350
, 550, S160, S170, Printex U, V, 140U, 140V, 9
5, 90, 85, 80, 75, 45, 40, P, 60, 300, 30, 35, 2
5, 200, A, G, L6, L (all made by Degussa), Regal41
5R, 330R, 250R, 995R, Monarch800, 880, 900, 460
, 280, 120 (or more, made by Cabot), Raven 850, 780
ULTRA, 760 ULTRA, 790 ULTRA, 520, 500, 410, 420
, 430, 450, 460, 890, 1020 (all manufactured by Columbia) and the like.

The carbon black used in the recording liquid of the present invention is obtained by chemically treating carbon black (oxidation treatment, fluorination treatment, etc.), dispersing agent, surfactant, etc. physically or chemically. Those which are chemically bonded (grafting treatment, one in which a dispersant is adsorbed in advance before dispersion) or the like may be used. It is preferable that the average particle size of carbon black in the recording liquid is in the range of 0.01 to 0.5 μm from the viewpoint of dispersion stability and ejection stability.
05-0.3 μm is more preferable, and 0.1-0.3 μm
Is particularly preferred. Further, the maximum large particle size of the carbon black is preferably 5 μm or less from the viewpoint of dispersion stability and discharge stability. The amount of carbon black used is preferably in the range of 2 to 15% by weight based on the total weight of the recording liquid,
% By weight is more preferred.

The recording liquid of the present invention is particularly suitable when an aqueous medium mainly composed of water is used, and it is preferable to add a water-soluble organic solvent to water. Examples of the water-soluble organic solvent include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, and polyethylene glycol (# 200, # 30).
0, # 400, # 500), glycerin, and ethylene oxide adducts of the above glycols (specific examples: Liponic EG-1)
(Trade names, manufactured by Lipochemical Co., Ltd.), alkyl ethers of the above glycols, N-methylpyrrolidone, 1,3
-Dimethylimidazolinone, thiodiglycol, 2-pyrrolidone, sulfolane, dimethylsulfoxide, diethanolamine, triethanolamine, methanol, ethanol, isopropanol and the like. The amount of the water-soluble organic solvent used in the recording liquid is usually in the range of 5 to 30% by weight, but 10 to 25% by weight is preferable in terms of storage stability.

[0013] In addition to the recording liquid of the present invention, various polymer compounds can be added as required. For example, a water-soluble polymer or a resin emulsion can be used as a dispersant or a binder. As the water-soluble polymer and resin emulsion, any of cationic, nonionic, anionic, and amphoteric types may be used, but carboxylic acid (salt),
Anionic polymers having an anionic water-soluble group such as sulfonic acid (salt) and phosphoric acid (salt) can be preferably used. Either a homopolymer or a copolymer can be used. In particular, when a copolymer is used, it is preferable to use a copolymer having a hydrophobic group and a hydrophilic group in terms of storage stability of a recording liquid, water resistance, and abrasion resistance. Examples of the hydrophobic group in the polymer compound include a functional group having an aromatic ring such as a phenyl group, a benzyl group, and a naphthyl group, an alkyl group having 4 or more carbon atoms, which may be branched or substituted, an alkenyl group, and an alkynyl group. Can be Specific examples of the water-soluble polymer used in the present invention and / or the polymer compound as a resin emulsion include, for example, as an anionic polymer,
Poly (meth) acrylic acid, poly (α-methyl) styrene sulfonic acid, (α-methyl) styrene / (meth) acrylic acid copolymer, (α-methyl) styrene / (meth) acrylic acid / (meth) acrylic Acid ester copolymer, (meth) acrylic acid / (meth) acrylic acid ester copolymer, (α-methyl) styrene / maleic acid copolymer,
(Α-methyl) styrene / maleic acid / (meth) acrylate copolymer, (α-methyl) styrene / maleic acid half-ester copolymer, (α-methyl) styrene / styrenesulfonic acid copolymer, vinyl Naphthalene / maleic acid copolymer, vinyl naphthalene / acrylic acid copolymer, naphthalene sulfonic acid formalin condensate,
Lignin sulfonic acid and salts thereof are exemplified. (Α-Methyl) styrene refers to α-methylstyrene and / or styrene, and (meth) acrylic acid refers to methacrylic acid and / or acrylic acid, and so on.

As the cationic polymer, any polymer having a cationic group such as a quaternary ammonium salt can be used. Specific examples of the nonionic polymer include:
Examples include a polyethylene oxide / polypropylene oxide random copolymer, a polyethylene oxide / polypropylene oxide block copolymer, polyacrylamide, polymethacrylamide, polyvinylpyrrolidone, polyvinyl alcohol, polyvinylamine, polyvinylamidine, and polyallylamine. Above all, these polymer compounds are preferably uncolored in order to obtain printed matter having good color tone and not flowing in water.
Maximum absorbance in the range of 780 nm is 0.05 g
^-1 · l · cm ^-1 or less is preferable, 0.01 g ^-1 ·
Those having l · cm ⁻¹ or less are particularly preferred.

The polymer has a weight average molecular weight of 100.
0 to 50,000 or less is preferable, but 2,000 to 30
2,000 or less, more preferably 2,000 or more and 20,000 or less. The polymer compound is preferably a graft polymer or a random polymer mainly in view of production cost, but a random polymer is particularly preferable.

The above anionic polymer compound is L
It can be used in the form of an alkali metal salt such as i, Na, K, or Cs, ammonia, dimethylamine, or an organic amine salt such as mono, di, or triethanolamine.

When a polymer compound is added, its amount is preferably from 0.01 to 10% by weight, more preferably from 0.3 to 5% by weight, based on the recording liquid. Further, when a pigment is used as a coloring material, 1 to 1 based on the weight of the pigment.
The addition of 100% by weight is preferable from the viewpoint of storage stability and ejection stability of the recording liquid, more preferably 3 to 50% by weight, and 5 to 50% by weight.
30% by weight is particularly preferred. In the recording liquid of the present invention, other additives such as a surface tension adjusting agent and a preservative may be used. Examples of the additives that can be used include anionic surfactants including various known ones, nonionic surfactants, cationic surfactants, and amphoteric surfactants.

Examples of the anionic surfactant include fatty acid salts, alkyl sulfate salts, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates, alkyl phosphates, and polyoxyethylene alkyl. Sulfate, polyoxyethylene alkylaryl sulfate, alkane sulfonate, polyoxyethylene alkyl phosphate, N-methyl-N-oleoyl-taurate, α-olefin sulfonate and the like. .

Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene derivatives, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid Esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, and the like. Nonionic additives having an alkylene oxide structure are preferred, among which ethylene oxide structures or nonionic additives having a propylene oxide structure have storage stability,
It is preferable in terms of print density, and among them, HLB is 9 to 17
Is more preferable. Those having an HLB of 10 to 16 are particularly preferred.

Specifically, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl Ether, polyoxyethylene stearyl ether, polyoxyethylene alkylamine, aminopolyoxyethylene, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stearate, polyoxyethylene sorbitan oleate , Naphthol ethylene oxide adduct, acetylene glycol ethylene oxide adduct, bisphenol A ethylene oxide adducts include polyoxyethylene polyoxypropylene block polymers.

Examples of the cationic surfactant and the amphoteric surfactant include alkylamine salts, quaternary ammonium salts, alkylbetaines, and aminooxides.

In the recording liquid of the present invention, in addition to the above components, a water-soluble resin and a fungicide (specific examples: ProxelBDN, BD20, GXL, LV, XL)
-2, TN (trade name, manufactured by Zeneca), a bactericide, a pH adjuster, urea and its derivatives, thiourea and its derivatives, and the like may be added as necessary. The viscosity of the recording liquid of the present invention is preferably 1 to 10 cP from the viewpoint of ejection stability, and 1 to 7 cP.
Is particularly preferred. The surface tension of the recording liquid is 20 to 60 d.
yne / cm is preferable in terms of quick drying property and ejection stability.
5-48 dyne / cm is particularly preferred.

As a disperser used for preparing the recording liquid of the present invention, a jet mill such as a nanomizer and an ultimizer which can be pulverized without using a medium is used in addition to a ball mill, a roll mill and a sand grind mill. A grind mill or a jet mill with less contamination from media is preferred. After this grinding and dispersion treatment, coarse particles are removed using a filter or a centrifuge. In addition, since the grinding and dispersion treatment can be efficiently performed by adjusting the concentration of the recording liquid, it is preferable to dilute the processing liquid prepared at a high concentration with an aqueous medium to adjust the concentration of the recording liquid.

These coloring materials, polymers, surfactants, water-soluble organic solvents, other additives and water-soluble organic solvents may be used alone, but depending on the case, two or more kinds may be used. By using together, further effects can be obtained. The recording liquid of the present invention can be used not only for recording on plain paper but also for recording on other recording liquids (coated paper, glossy paper, synthetic paper, OHP sheets, etc.).

[0025]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto. In the following examples, “parts” and “%” are based on weight.

Example 1 (Preparation of recording liquid)

[0027]

[Table 1] Composition of recording liquid Amount (parts) Furnace Carbon Black manufactured by Mitsubishi Chemical Corporation (DBP oil absorption 147 ml / 100 g, volatile matter 3.7% by weight, pH 7.3, BET specific surface area 294 m ² / g) 4 Styrene / Na salt aqueous solution of acrylamide-2-methylpropanesulfonic acid / acrylic acid copolymer (solid content 30%) 2,1,3-dimethylimidazolidinone 4 ion-exchanged water 34 ────────────────── Total 44

Each of the above components was placed in a cylindrical stainless steel container and subjected to a dispersion treatment for 3 hours using a sand grinder together with 152 parts of zirconia beads (product of Toray) having an average diameter of 0.5 mm. To the obtained solution, 7 parts of xylitol, 3 parts of ethanol, and 46 parts of ion-exchanged water were added. This solution was Pressure filtration was performed using a 5C filter paper, and the liquid obtained here was used as a recording liquid. (Measurement of Particle Size Distribution) The obtained recording liquid was subjected to particle size distribution measurement with a particle size distribution meter (MicrotracUPA (Nikkiso sales)) at the same concentration.

[0029]

[Table 2] Measurement conditions Transparent Particles: No, Spherical Particles:
No Particle Refractive Index: 1.81 Particle Density: 1.86 Fluid Refractive Index: 1.33 High Temp: 30.0 ℃ Viscosity: 0.797 cP Low Temp: 20.0 ℃ Viscosity: 1.002 cP Run Time: 300 (sec), Number of Runs: 2

The average value of the two measurements under the above measurement conditions was taken as the value of the particle size distribution of the recording liquid, and
% Diameter (D50) was defined as the average particle diameter of the recording liquid. The average particle size was 0.163 μm.

(Printing test) The recording liquid obtained by the method described in the above example was applied to an electrophotographic paper (Xerox 4024 paper, Xerx paper) using a Hewlett-Packard printer.
ox product), a stable and good ejection property without clogging or the like was obtained, and a printed matter having good print quality was obtained.

(Evaluation of Print Density) The density OD of the printed matter obtained in the above print test was measured using a Macbeth reflection densitometer (RD914). The results were ○ when classified as follows.

[0033]

[Table 3] ○: OD 1.3 or more △: OD 1.2 or more and less than 1.3 ×: OD less than 1.2

(Storage stability test)
After storage at room temperature for 1 week, the temperature was returned to room temperature after storage, and the presence or absence of aggregates in the recording solution was visually judged. As a result, no aggregates were confirmed.

[0035]

According to the present invention, it is possible to obtain a recording liquid which is excellent in storage stability and ejection stability, has high moisturizing properties and does not cause clogging of nozzles, for ink jet recording or for writing implements. Further, printed matter using the recording liquid has good print quality and good fastness such as light fastness and water fastness.

 ──────────────────────────────────────────────────続 き Continued on front page F term (reference) 2C056 EA13 FC01 2H086 BA52 BA53 BA55 BA60 BA62 4J039 AD02 AD03 AD09 AD10 AD14 AD22 BA04 BC07 BC09 BC12 BC13 BC35 BC36 BC37 BC50 BC51 BC54 BC55 BC60 BE01 BE04 BE06 BE07 BE08 BE12 BE22 CA03 CA06 EA15 EA16 EA17 EA19 EA35 EA38 EA41 EA42 EA44 GA24

Claims (10)

[Claims] 1. A recording liquid containing xylitol. 2. The recording liquid according to claim 1, wherein the recording liquid contains 0.3 to 30% by weight. 3. The recording liquid according to claim 1, wherein the recording liquid is a recording liquid containing a coloring material in an aqueous medium. 4. The recording liquid according to claim 3, wherein carbon black is used as a coloring material. 5. The carbon black has a DBP oil absorption of 14
The recording liquid according to claim 4, wherein the amount is 0 to 300 ml / 100 g. 6. A recording liquid containing 2 to 1 carbon black.
The recording liquid according to claim 4, wherein the recording liquid is contained in an amount of 5% by weight. 7. The recording liquid according to claim 3, wherein the recording liquid further contains a polymer compound. 8. The recording liquid contains a polymer compound in an amount of 0.01 to 0.01.
The recording liquid according to claim 7, wherein the recording liquid is contained in an amount of 10% by weight. 9. An ink jet recording liquid using the recording liquid according to claim 1. Description: 10. An ink jet recording method for performing recording by discharging a recording liquid, wherein the recording liquid for ink jet according to claim 9 is used as the recording liquid.