JP3235291B2 - Inkjet recording liquid and recording method using this recording liquid - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ink jet recording liquid used for an ink jet printer and a recording method using the recording liquid.

[0002]

2. Description of the Related Art An ink jet printer ejects ink from minute nozzles to record characters, figures and pictures on paper. Both aqueous and non-aqueous ink jet recording liquids are used for such printers, and basically, it is required to have the following characteristics.

[0003] The ink jet device is stable against long-term storage and does not cause clogging.

[0004] Fixing to an image recording material (paper, film, etc.) is fast and reliable, and the periphery of the dot is smooth and has little blur.

The color tone of the formed recorded image is clear and high in density.

[0006] The formed recorded image is excellent in water resistance and light resistance.

[0007] The formed recording image has good fixability without causing a decrease in density or smearing due to rubbing.

[0008] The recording liquid peripheral material (container, connecting tube, seal material, etc.) must not be affected.

Low odor and toxicity, and excellent in safety such as flammability.

However, the water-based ink has low odor and toxicity, and is excellent in safety such as flammability. However, since the water-based ink mainly contains a water-soluble dye, the obtained recorded image depends on the physical properties of the water-soluble dye. As a result, it is inferior in its water resistance and light resistance. In order to avoid the problem, those using pigments instead of dyes are difficult to disperse finely and uniformly and have poor storage stability because the pigments are insoluble in water. Further, there is a problem that water is easily evaporated and clogging is likely to occur at a discharge portion of the ink jet device. In addition, both of them have a problem in that the obtained recorded images are rubbed, resulting in a decrease in density and stains.

[0011]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a recording liquid which has good dispersibility of color material particles, does not cause dry clogging, and has excellent fixability. Aim.

A further object of the present invention is to provide an ink jet recording liquid capable of forming an excellent recorded image without bleeding even when high density printing is performed. Another object of the present invention is to provide a recording method capable of obtaining a recorded image having excellent fixability.

[0013]

SUMMARY OF THE INVENTION The present invention relates to a method for producing a resin having a boiling point of 150.degree.
A dispersion medium comprising the above non-aqueous solvent; and a dispersion medium dispersed in the dispersion medium, comprising a colorant and a resin.
0% by weight of colorant particles, 0.01 to 10% by weight of a resin soluble in the dispersion medium, and 0.001 to 5% by weight of Borneo
And an ink jet recording liquid containing the same. Further, the present invention relates to a non-aqueous solvent having a boiling point of 150 ° C. or higher.
And a dispersion medium, dispersed in the dispersion medium, a colorant and
Color material particles composed of resin and having an addition amount of 1 to 20% by weight
And 0.01 to 10% by weight of a resin soluble in the dispersion medium.
And 0.001 to 5% by weight of alginate,
The present invention relates to an ink jet recording liquid containing no water. Ma
Further, the present invention comprises a non-aqueous solvent having a boiling point of 150 ° C. or higher.
A dispersion medium, dispersed in the dispersion medium, a colorant and a resin
Coloring material particles comprising 1 to 20% by weight,
0.01 to 10% by weight of a resin soluble in the dispersion medium,
0.001 to 5% by weight of alginate and 7 to 50% by weight
% Of water and ink-jet recording liquid
You. In addition, the present invention relates to a recording method in which the recording liquid is heated and fixed after printing on recording paper with the above-described recording liquid for inkjet.

In the present invention, the recording liquid comprising the above composition is a uniform solution in which the coloring material particles are dispersed and the other components are dissolved or compatible, and is excellent in fixability, storage stability and stability. By including at least one type of additive in a predetermined amount, in addition to the above-described effects, a recording liquid having excellent dispersibility of color material particles can be obtained, and an excellent recorded image without bleeding or show-through can be formed. Can be.

The ink jet recording liquid of the present invention comprises at least a dispersion medium, coloring material particles, resin and additives.

As the dispersion medium, a non-aqueous solvent is used. Non-aqueous solvents are solvents other than water. Among these non-aqueous solvents, those having a boiling point of 150 ° C. or higher, preferably 180 ° C. or higher are used. If the boiling point is lower than 150 ° C., problems such as poor dispersion, precipitation of agglomerates, and clogging of nozzles are likely to occur because the evaporation rate is high. When water is added to the dispersion medium, it is preferable to use a solvent compatible with water. Specifically, alkyl ethers of (mono, di, tri, tetra) alkylene glycols, for example, ethylene glycol monoalkyl ether (bp 150 to 250
° C), diethylene glycol monoalkyl ether (b
150-250 ° C), triethylene glycol monoalkyl ether (bp 249-300 ° C), propylene glycol monoalkyl ether (bp 190-250)
C), tripropylene glycol monoalkyl ethers (bp 243 to 300 ° C), (mono, di, tri) alkylene glycols (bp 150 to 300 ° C) and the like.
p150-300 ° C), pyrrolidones such as 2-pyrrolidone (bp 245 ° C), N-methylpyrrolidone (bp
202 ° C.) and mixtures thereof.

In addition, heterocyclic alcohols, phenols, pyrrolidones, ester solvents (adipate, azelate, sebacate, maleate, fumarate, phosphate, ricinoleate, heterocyclic ester), etc., having a boiling point of 150 ° C. or more A thing may be used.

Among these, (mono, di, tri) ethylene glycol monobutyl ether, (mono, di, tri)
Propylene glycol monobutyl ether, butyl cellosolve, and 2-pyrrolidone are preferred from the viewpoints of dispersibility of the coloring material particles, solubility of the resin, printability, maintainability of the ink jet head, and the like.

The above-mentioned non-aqueous solvent is desirably contained in the recording liquid in an amount of 55% by weight or more when water is not added to the recording liquid, and preferably in an amount of 40% by weight or more in the recording liquid when water is added.

In the present invention, it is preferable to add water to the recording liquid. By using a water-compatible non-aqueous solvent and water in combination, it is possible to increase the drying speed of the ink when printing and prevent the ink from bleeding.
The amount of water to be added is 7 to 50% by weight of the recording liquid composition,
Preferably, it is about 10 to 45% by weight. If it is less than 7% by weight, the effect of addition cannot be obtained. At 50% by weight or more,
There is a possibility that the fixing speed of the recording paper becomes slow and offset to another paper. Further, the addition of water is necessary for the jet ink of the bubble jet type, and is useful when the recording liquid may be ignited.

As the colorant particles used in the recording liquid of the present invention, resin particles obtained by dispersing a pigment or a dye, or microcapsule resin particles containing a pigment or a dye can be used. Examples of the microcapsule resin particles include, for example, JP-A-59-65854 and JP-A-60-88.
No. 956, JP-A-60-254049, JP-A-62-283346, JP-A-62-28334
No. 7, JP-A-63-32559 and the like can be used. Further, as the microcapsule resin particles, those containing a liquid as a core material are preferable.

It is desirable to use color material particles having an average particle size of 5 μm or less, preferably 0.01 to 2 μm.

As the pigment that can be used for the coloring material particles, all kinds of organic or inorganic pigments including conventionally known pigments can be used. For example, azo, phthalocyanine, quinacridone, anthraquinone, dioxazine, indigo, benzidine, thioindico, perinone, perylene, isoindolenone, titanium oxide, cadmium, iron oxide, carbon black, etc. Can be mentioned.

The materials having excellent properties as pigments usable in the present invention are shown below by color index (CI) numbers.

C. I. As yellow pigments, 13, 24,
86, 93, 94, 108, 109, 110, 117,
125, 137, 138, 147, 153, 154, 1
66, 168 and the like. C. I. Examples of the orange pigment include 36, 43, 51, 55, 59, 61 and the like. C. I. As the red pigment, 97, 122, 1
23, 149, 168, 177, 178, 180, 18
7, 190, 192, 209, 215, 216, 21
7, 220, 223, 224, 226, 227, 22
8, 240 and the like. C. I. As violet pigments, 19, 23, 29, 30, 37, 40, 50
And the like. C. I. As blue pigments, 15, 1
5: 1, 15: 3, 15: 4, 15: 6, 22, 60,
64 and the like. C. I. As the green pigment, 7,
36 and the like. C. I. As brown pigment,
23, 25, 26 and the like. C. I. Examples of the black pigment include 7, 1 and the like.

These pigments can be used in a state of being dissolved or insoluble in the above-mentioned solvent, but generally they are not dissolved.

As the dye that can be used for the coloring material particles, all kinds of natural and synthetic dyes including conventionally known dyes can be used. For example, nitroso, nitro, azo, stilbene, diphenylmethane, triarylmethane,
Zansen type, acridine type, quinoline type, methine type, polymethine type, thiazole type, indamine type, indophenol type, azine type, oxazine type, thiazine type, sulfurized type, aminoketone type, oxyketone type, anthraquinone type, Indigo-based and phthalocyanine-based dyes can be used.

The coloring material particles are contained in the recording liquid composition in an amount of from 1 to 2
When the content is 0% by weight, preferably 1.5 to 15% by weight, and 1% by weight or less, the concentration is too low, which is not preferable as a recording liquid. When used in an amount of 20% by weight or more, the dispersibility deteriorates, thixotropic properties are developed,
Disturbs ink ejection.

As described above, an image is formed using the coloring material particles containing the resin, and the image is heat-fixed or pressure-fixed, whereby a recorded image having excellent fixing strength can be obtained.

Further, it is also possible to use microcapsule particles containing a photocuring agent as coloring material particles and to irradiate the obtained image with light to perform photocuring, thereby improving the fixing strength of the recorded image. is there.

For example, as a photocuring agent, cinnamic acid ester group, cinnamylidene group, β-styrylacryl group, acroyl group, bisacrylamide group, styrylpyridinium group, benzalacetophenone group, maleimide group, pyridine-N-oxide group, Quinoline-N-oxide group, N
A photocurable polymer in which an allyloxymethyl group or the like is bonded to polyvinyl alcohol, poly-p-vinylphenol, or the like via an ester or methylol group.
Moreover, you may use the photocurable coating material by radical polymerization. Photocurable coatings include unsaturated polyester type and acrylic side chain type, and both of them are photocured when a sensitizer is added. Vinyl monomers such as styrene and α-methylstyrene which are easily copolymerized with these acrylated polymers and oligomers, divinyl monomers such as ethylene glycol and diethylene glycol methacrylate, or trimethylol
A paint is prepared by mixing tri- and tetravinyl monomers such as luethane acrylate and tetramethyl methane acrylate. Unsaturated polyester type is maleic anhydride,
Unsaturated polyesters such as fumaric acid, metaconic acid, citraconic acid and chlorinated maleic acid, ethylene glycol, diethylene glycol, 1,2-propylene glycol,
It is composed of 1,3-butylene glycol, bisphenoldioxyethyl ether, neopentyl glycol, butanediol, and the like. The acrylic side chain type is composed of a monomer having epoxy, urethane, ester, polyether and the like and an acrylic monomer.

As the photopolymerization initiator, near ultraviolet 300 to 4
Compounds having absorption around 50 nm, for example, benzoin methyl ether, isopropyl ether, benzoin and the like can be used. Also, 5-nitrofluorene, 5-nitroacenaphthene, and cobalt naphthenate can be used in combination as a photosensitizer. The photocuring agent is desirably added in a capsule of 0.01 to 5% by weight.

The resin used in the ink jet recording liquid of the present invention is dissolved in the recording liquid and is present. The resin enhances the dispersibility of the above color material particles and improves the fixability of the printed ink to the recording paper. It works to improve and prevent the spread of ink. Such resins include butyral resins such as polyvinyl butyral, acrylic resins such as water-soluble acrylic resins, alkylene glycol resins such as polyethylene glycol, rosin resins, vinyl alcohol resins such as polyethylene glycol, and polyvinylpyrrolidone resins. It is. In particular, butyral resin,
Water-soluble acrylic resins, polyvinyl alcohol, polyvinyl pyrrolidone, and polyethylene glycol are preferred. When a butyral resin is used, the molecular weight is 2,000.
~ 100,000, preferably 3,000 ~ 10,000
It is desirable to use 0 from the viewpoint of dispersion stability. When water is added to the recording liquid, it is desirable to use a water-soluble resin as the resin. These resins are used in the ink composition in an amount of 0.01 to 10% by weight, preferably 0.05 to 8% by weight, and more preferably 0.1 to 7% by weight. When the amount is less than 0.01% by weight, the dispersion stability of the ink is deteriorated. When the amount is more than 10% by weight, the viscosity of the ink becomes too high.
Agglomeration of color material particles is observed.

The additives used in the ink jet recording liquid of the present invention include alginate and borneo
At least one selected from the group consisting of These additives dissolve and exist in the recording liquid, improve the dispersibility of the recording liquid, and particularly effectively work to prevent the bleeding of the ink onto the recording paper and the show-through. As alginate, for example, metal alginate, ammonium alginate and the like, and as borneols, for example, borneol, isoborneol and the like can be used.

These additives are used in the recording liquid composition in an amount of 0.0
It is added in an amount of 0.01 to 5% by weight, preferably 0.003 to 4.5% by weight, and more preferably 0.05 to 4% by weight. If the amount is less than 0.001% by weight, ink bleeds and show-through becomes noticeable. If it is more than 5% by weight, the viscosity of the recording liquid increases, the fluidity becomes poor, and the dispersibility is also adversely affected.

In the present invention, other additives such as a humectant, an emulsifier, an anti-drying agent and the like may be appropriately added. Specifically, humectants such as aliphatic alcohol amines (such as triethanolamine), alkylamines (such as triethylamine) and lower aliphatic alcohols (such as ethanol, propanol and hexal), aromatic polyglycol ethers and alkylaryl polyglycol ethers ,
Emulsifiers such as sorbitan monooleate; and drying inhibitors such as alkyl naphthalene sulfonate and alkyl aryl sulfonate. When these additives are used, they are added in an amount of about 0.05 to 5% by weight in the recording liquid composition. If the amount is less than 0.05% by weight, the effect of the addition is not obtained. If the amount is more than 5% by weight, the composition of the recording liquid is liable to change due to the ease of evaporation, resulting in poor storage stability. Will be lacking. The additives are selected so as to be dissolved in the recording liquid.

In the present invention, other additives such as 2,2'-thiodiethanol, formamide, glycerin, ethylene carbonate, and methanesulfonic acid may be used in accordance with the type and type of the ink jet printer. The additives have a function of preventing bleeding, feathering and show-through of a printed image.

The ink jet recording liquid of the present invention is produced by mixing, stirring and kneading the above-mentioned materials using a stirrer. During the production, if necessary, a resin, a solvent, a dispersant, etc. may be added again, or in an optional step or as a final step, filtration may be performed to remove coarse particles, or in a low vacuum. For defoaming.

As a specific device, a ball mill pot,
Commercially available products such as a paint conditioner, a circulation type ultrasonic homogenizer, a sand mill, an ultrasonic dispersion device, and a roll mill can be used.

However, it is preferable to prepare the recording liquid in a clean and dry atmosphere from the viewpoints of production stability and ink ejection stability. Further, when the above process is performed while maintaining the entire apparatus at a constant temperature, a recording liquid having more excellent dispersion stability can be obtained.

The viscosity of the ink jet recording liquid finally obtained is adjusted to a viscosity suitable for each ink jet system. As the inkjet method, continuous ejection type (continuous type), volume change ejection type (piezo type), electrostatic type, bubble jet (thermal inkjet type)
Etc. are known. The viscosity and surface tension can be adjusted by selecting the type, combination, ratio, and the like of the composition.

In the case of a continuous discharge type (continuous type), the viscosity is 2.2 to 20 cp, preferably 2.5 to 10 cp.
cp and the surface tension are adjusted to 15 to 65 dyne / cm, preferably 20 to 60 dyne / cm. 20cp viscosity
If it is higher, the recording liquid will not easily come out of the nozzle, and if the surface tension is lower than 15 dyne / cm, liquid dripping will occur.

In the case of the volume change discharge method, the viscosity is 2.2 to 3
0 cp, preferably 2.5 to 20 cp with a surface tension of 20 to 20 cp.
60 dyne / cm, preferably 25-60 dyne /
Adjust to cm. If it is higher than 30 cp, the recording liquid cannot be sufficiently supplied, and if it is lower than 20 dyne / cm, liquid dripping occurs.

In the case of the electrostatic type, the viscosity is 2.2 to 40 cp, preferably 2.5 to 30 cp, and the surface tension is 15 to 60 dy.
ne / cm, preferably 20 to 55 dyne / cm. When the viscosity is higher than 40 cp, it is difficult for the liquid to come out of the slit nozzle, and when the viscosity is lower than 15 dyne / cm, liquid dripping occurs.

In the case of the bubble jet type, the viscosity is 2.2.
-30, preferably 2.5-20 cp, with a surface tension of 15
６５65, preferably 20 to 60 dyne / cm.

If the viscosity is higher than 30 cp, the recording liquid cannot be supplied sufficiently, and it becomes difficult for the recording liquid to come out of the nozzle. If the surface tension is lower than 15 dyne / cm, liquid dripping occurs.

In the case of the thermal / electrostatic method described in Japanese Patent Application No. 3-296797, the viscosity is 4 to 200, preferably 4 to 1.
Surface tension 25-55, preferably 25-5
Adjust to 0 dyne / cm. If the viscosity is higher than 200 cp, it becomes difficult to eject ink.

The lower limit of the viscosity and the upper limit of the surface tension of each recording liquid are limited by the composition.

[0049]

【Example】

(Production Example of Coloring Material Particles 1) 90 g of methylene chloride was placed in a 200 ml beaker, and a pigment (carbon black:
(MOGUL L: Cabot) 2 g of high molecular weight polyester and 20 g of high molecular weight polyester are added with stirring and dissolved at room temperature in advance to prepare a polymer solution. In addition, 500m of water is added to 1L beaker.
of sodium dodecylbenzenesulfonate.
5 g and a cellulose derivative (Metrozu 655H-50:
(Shin-Etsu Chemical Co., Ltd.) was added and stirred for 2 hours without applying heat to completely dissolve, thereby preparing an aqueous dispersion. Then 50
200 ml of the above aqueous dispersion is placed in a 0 ml beaker and stirred at 9000 rpm using a homomixer. The polymer solution prepared in advance is added thereto and stirred for 10 minutes. Thereafter, the mixture was heated for 2 hours while being slowly stirred at 200 revolutions per minute by a three-one motor to remove methylene chloride in the liquid to obtain coloring material particles 1 having a volume average particle diameter of 1.5 μm.

(Production Example of Color Material Particles 2) In the production example of the color material particles 1, dye (Diacot) was used instead of carbon black.
(TonFast Black D: Mitsubishi Kasei Kogyo Co., Ltd.) Except for using 2.0 g, color material particles 2 having a volume average particle diameter of 0.9 μm were obtained.

(Production Example of Color Material Particles 3) In the same manner as in the production example of the color material particles 1, except that 3.0 g of MA-8 (Mitsubishi Chemical Industry Co., Ltd.) was used as the carbon black, the volume average particle diameter was 1 0.4 μm color material particles 3 were obtained.

(Production Example of Color Material Particles 4) In the production example of the color material particles 1, a dye (Nigros
(ineNB conc .: Sumitomo Chemical Co., Ltd.) Except for using 3.0 g, color material particles 4 having a volume average particle diameter of 1.0 μm were obtained.

(Production Example of Color Material Particles 5) In the production example of the color material particles 1, carbon black was added to RAVEN1020.
(Colombian Carbon Co., Ltd.) Color material particles 5 having a volume average particle size of 1.5 μm were obtained in the same manner except that 2.5 g was used.

(Production Example of Color Material Particles 6) In the production example of the color material particles 1, a dye (Nigros
(ineBR: Orient Chemical Co., Ltd.) Coloring material particles 6 having a volume average particle size of 0.8 μm were obtained in the same manner except that 2.5 g was used.

(Production Example of Coloring Material Particles 7) 50 g of tridecyl methacrylate, 30 g of n-butyl methacrylate, 80 g of silicone oil SH-556 (Toray Silicone Co., Ltd.),
Catalyst 2,2'-azobisisobutyronitrol 0.5 g,
5 g of the dye Oil Blue A (Du Pont) was placed in a ball mill and mixed for 3 hours to prepare a blue ink. 20 g of Takenate D-102 (Takeda Pharmaceutical Co., Ltd.) was added to the above mixture, and after stirring, the mixture was emulsified and dispersed in 1 liter of a 10% aqueous solution of gum arabic at 9000 rpm with an auto homomixer (Tokuki Kiko Co., Ltd.). After adjusting the average size of the emulsified oil droplets to bake 1.2 μm, a 10% aqueous solution of hexamethylenediamine 30 was prepared.
g was added dropwise, and then the temperature was raised to 50 ° C. at 4500 rpm and stirred for 2 hours, and then stirred at 75 ° C. for 6 hours to complete the encapsulation. The obtained capsule particles were precipitated by gravity sedimentation, and the supernatant was replaced with water. After such an operation was repeated 6 to 8 times, the mixture was filtered, placed in an oven at 60 ° C., and dried for 8 hours to obtain color material particles 7 having a volume average particle diameter of 1.3 μm.

(Production Example of Color Material Particles 8) Color material particles 8 were produced in the same manner as in the production example of color material particles 7 except that copper phthalocyanine blue pigment (Pigmentable-15) was used in place of dye Oil Blue A. I got

(Production Example of Color Material Particles 9) In the production example of the color material particles 7, Aizen Primula was used in place of the dye Oil Blue A.
Color material particles 9 were obtained in the same manner except that 6 g of Red 4BH (Hodogaya Chemical Co., Ltd.) was used.

(Production Example of Color Material Particles 10) The color material particles 10 were produced in the same manner as in the production example of the color material particles 7 except that 6 g of quinacridone red pigment (Pigment Red 122) was used in place of the dye Oil Blue A. Obtained.

(Production Example of Color Material Particles 11) In the production example of the color material particles 7, Solar Yellow was used in place of the dye Oil Blue A.
Color material particles 11 were obtained in the same manner except that 6.5 g of 3LG (Sandoz Ltd.) was used.

(Production Example of Color Material Particles 12) A color material was produced in the same manner as in the production example of the color material particles 7 except that 6.5 g of a benzidine yellow pigment (Pigment Yellow-13) was used instead of the dye Oil Blue A. Particles 12 were obtained.

(Production Example of Coloring Material Particles 13) 50 g of tridecyl methacrylate, 30 g of n-butyl methacrylate, silicone oil SH-556 (Toray Silicone Co., Ltd.) 80
g, catalyst 2,2'-azobisisobutyronitrol 0.5
g, 5 g of dye Oil Blue A (Du Pont) and 1 g of vinyl carbazole-triethylamine as a photocuring agent were placed in a ball mill and mixed for 3 hours to prepare a blue ink. To the mixture was added 20 g of Takenate D-102 (Takeda Pharmaceutical Co., Ltd.), and after stirring, 9000 r of auto homomixer (Special Kiko Co., Ltd.) was added to 1 liter of 10% arabic gum aqueous solution.
It was emulsified and dispersed at pm. After adjusting the average size of the emulsified oil droplets to bake 1.8 μm, 30 g of a 10% aqueous solution of hexamethylenediamine was added dropwise, and then 4000 rpm
At 50 ° C. and stirred for 2 hours.
Stir for hours to complete the encapsulation. The obtained capsule particles were precipitated by gravity sedimentation, and the supernatant was replaced with water. After such an operation was repeated 6 to 8 times, the mixture was filtered, placed in an oven at 60 ° C., and dried for 8 hours to obtain color material particles 13 having a volume average particle size of 2.0 μm.

[0062] The solvent shown in Table 1 to Table 4 below (Preparation of ink), colorant particles, a dispersant,
For each of Examples 1 to 5 , each additive was treated with a paint conditioner (manufactured by Red Devil Co., Ltd.) for 4 hours .
9 for 2 hours with a circulating ultrasonic homogenizer (manufactured by Nippon Seiki Co., Ltd.), and for Examples 10 to 12 , 1.5 hours with an ultrasonic dispersion UT-20 (manufactured by Shinmeidai Industry Co., Ltd.) for Examples 13 to 16. About 3 hours with a paint conditioner (manufactured by Red Devil Co.), and Comparative Examples 1 to 5 were obtained with 4 hours using a paint conditioner (manufactured by Red Devil).
The treatment was performed for each time.

In the table, the numbers in brackets [] indicate the weight% with respect to the recording liquid.

[0064]

[Table 1]

[0065]

[Table 2]

[0066]

[Table 3]

[0067]

[Table 4]

[0068]

[Table 5]

[0069]

[Table 6]

(Evaluation of Ink) The ink obtained as described above was evaluated for viscosity, dispersibility, bleeding, show-through, fixing speed, light fastness, density, water fastness, and fixing strength as follows. Table 7 shows the results
And Table 8 .

(Viscosity): Precision viscometer (model: Low shear)
30, Contraves). that time,
The test was carried out at a constant temperature of 25 ° C.

Further, the change in viscosity when a shear (shear stress) was applied was measured to evaluate the dependency of the viscosity on the shear rate. For example, when there is a relationship between the viscosity and the shear rate as shown in FIG. 1 (a), the shear rate dependency indicates that the dispersibility is good, and the relationship as shown in FIG. 1 (b). Some cases indicate poor dispersibility.

(Surface tension): Surface tensiometer (model: CBV)
P-A3, manufactured by Interface Science Co., Ltd.). At that time, the temperature was set at 25 ° C. in a constant environment.

(Dispersibility): The dispersibility was evaluated by measuring the viscosity and the shear rate dependency as described above. That is, thermal shock (−20 ° C.)
(A heat cycle of 90 ° C. was performed 4 times / day, and each temperature was kept for 1 hour), and changes in the graph before and after that were examined. The evaluation was ranked as follows.

：: No change before and after the test, indicating good dispersion stability.

×: There is a change before and after the test, and separation and aggregation occur when stored for a long time.

(Bleeding): Evaluation was performed using a Minolta original evaluation machine using a commercially available XY plotter (with a program function) and a plotter pen. That is, a plotter pen tip (inner diameter 0.1, 0.2, 0.3, 0.5 m
m) and a microdispenser, draw a line with a plotter in a non-contact state with the paper while quantitatively supplying ink to the pen tip, and measure the spread (bleed) with respect to the inner diameter width,
Ranking was performed as follows. The paper used at this time is plain paper EP paper for Minolta camera copiers.

◎: Spreading rate: 0 to less than 10% ：: Spreading rate: less than 10 to 20% Δ: Spreading rate: less than 20 to 30% X: Spreading rate: 30% or more (Offset): Bleeding was measured. In the same manner as above, the pen inner diameter was fixed at 0.5 mm, a black solid pattern of 5 mm square was drawn on paper, and the value obtained by subtracting the reflection density of only the paper from the reflection density measurement value on the back surface was measured. It was ranked as follows. However, the reflection density was measured by the Sakura densitometer PDA-65.
(Manufactured by Konishi Roku Photo Industry Co., Ltd.).

◎: less than 0.1 ：: 0.1 to less than 0.2 Δ: 0.2 to less than 0.3 ×: 0.3 or more Desirably rank “○” or more.

(Fixing speed): A solid black pattern was drawn in the same manner as in the show-through evaluation. Immediately after that, a polyurethane blade (a cleaning blade of a copying machine manufactured by Minolta) was scanned with no weight like a wiper, and ink was wiped off. The time until no longer appeared was measured and ranked as follows.

◎: less than 2.5 seconds ：: less than 2.5 to 5 seconds Δ: less than 5 to 10 seconds ×: 10 seconds or more Rank “「 ”or more is desirable.

(Light fastness): A solid black pattern was drawn in the same manner as in the show-through evaluation, and the initial reflection density (I ₀ ) was measured. Thereafter, exposure was performed for 200 hours under a fluorescent light of 5000 lux to deteriorate the light, and the reflection density (I ₁ ) was measured again. I ₁ / I
The ratio of ₀ (%) was calculated and evaluated as follows.

◎: 100 to 98% or more ：: Less than 98% to 96% or more Δ: Less than 96% to 94% or more ×: Less than 94% Rank “○” or more is desirable.

(Density): A solid black pattern was drawn in the same manner as in the show-through evaluation, and a reflection densitometer (Sakura densitometer PDA) was used.
-65, manufactured by Konica Corporation), and the image density was evaluated as follows.

◎: 1.2 or more ○: less than 1.2 to 1.0 Δ: less than 1.0 Rank “○” or more is preferable.

(Water resistance): A solid black pattern was drawn in the same manner as in the show-through evaluation, and immersed in pure water for 10 minutes. Thereafter, it was dried and the image density was measured. The decrease from the initial value was calculated and evaluated as follows.

◎: less than 0.1 ：: 0.1 or more to less than 0.2 Δ: 0.2 or more to less than 0.3 ×: 0.3 or more Rank “○” or more is preferable.

(Fixing strength): 5 mm on plain paper EP paper for Minolta camera copier by volume change discharge method.
After printing the solid pattern of the corner, the ink using the color material particles 1 to 6 is heated and fixed by passing through a fixing device (fixing temperature set to 100 ° C.) of a copying machine EP-4321 (manufactured by Minolta Camera Co., Ltd.). For inks using color material particles 7 to 12, Family Copier PC-30 (manufactured by Canon Inc.)
Pressure fixing unit to perform pressure fixing.
After the ink using No. 3 was irradiated with an ultraviolet lamp of 100 W, fixing was performed through a pair of rollers (SUS roller, 3 kg with respect to the width of the weight A4). Vertically cut sand eraser (No. 502: manufactured by Lion Corporation) was pressed against the obtained fixed image with a load of 1000 g at an angle of 45 °, and the reflection density of the image before and after three reciprocations at a speed of 2 cm / sec was measured. It was measured with a Sakura densitometer (Sakura Densitometer PDA65), and the change in concentration was evaluated as follows.

◎: less than 5% decrease in density ○: less than 10% decrease in density Δ: less than 30% decrease in density ×: 30% or more decrease in density

[0090]

[Table 7]

[0091]

[Table 8]

[0092]

[0093]

According to the ink jet recording liquid of the present invention, a recorded image having an excellent fixing strength can be obtained.

Further, the ink jet recording liquid of the present invention comprises:
Excellent dispersibility, no bleeding of print image, no show-through, etc.
Further, according to the recording method of the present invention, a recorded image having excellent fixing strength can be obtained.

[Brief description of the drawings]

FIG. 1 is a diagram for explaining the relationship between viscosity and shear rate.

──────────────────────────────────────────────────続 き Continuation of front page (56) References JP-A-60-92368 (JP, A) JP-A-63-210181 (JP, A) JP-A-54-62005 (JP, A) JP-A-4- 132774 (JP, A) JP-A-4-185672 (JP, A) JP-A-4-185674 (JP, A) JP-A-59-182860 (JP, A) JP-A-5-295310 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C09D 11/00-11/20

Claims (4)

(57) [Claims] 1. A dispersion medium comprising a non-aqueous solvent having a boiling point of 150 ° C. or higher, and coloring material particles dispersed in the dispersion medium, comprising a colorant and a resin, and having an addition amount of 1 to 20% by weight,
0.01 to 10% by weight of a resin soluble in the dispersion medium,
An ink-jet recording liquid comprising 0.001 to 5% by weight of borneols . 2. A non-aqueous solvent having a boiling point of 150 ° C. or higher.
A dispersion medium, dispersed in the dispersion medium, a colorant and a resin
Coloring material particles comprising 1 to 20% by weight,
0.01 to 10% by weight of a resin soluble in the dispersion medium,
0.001 to 5% by weight of alginate and water
A recording liquid for inkjet, characterized by not containing. 3. A non-aqueous solvent having a boiling point of 150 ° C. or higher.
A dispersion medium, dispersed in the dispersion medium, a colorant and a resin
Coloring material particles comprising 1 to 20% by weight,
0.01 to 10% by weight of a resin soluble in the dispersion medium,
0.001 to 5% by weight of alginate and 7 to 50% by weight
% Water.
Recording liquid. 4. The ink jet according to claim 1,
After printing on recording paper with the jet recording liquid, heat fix
A recording method characterized in that: