JPH0641483A - Recording liquid, methd for liquid jet recording, and apparatus using such recording liquid - Google Patents

Abstract

PURPOSE:To obtain a recording liq. which gives a printed image having excellent characteristics when used for printing on a coated paper, a plain paper, a regenerated paper, etc., by compounding a liq. dispersion of protein into the liq. CONSTITUTION:The recording liq. contains a liq. dispersion obtd. by dispersing a water-insol. protein using a water-sol. protein pref. in a ratio of the former protein to the latter of (10:1)-(1:1). The amt. of the dispersion contained is 0.1% or higher, pref. 0.5-10%, in terms of solid. A fibrous protein and/or its deriv. is pref. The recording liq. pref. has a pH of 4.0-10 and is esp. for liq. jet recording.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a recording liquid, a liquid jet recording method using the recording liquid, and an apparatus using the recording liquid.

[0002]

2. Description of the Related Art Conventionally, various reports have been made on recording liquids for liquid jet recording apparatuses, not only in monochrome but also in the color field. For example, in the past, there have been many studies on the relationship with coated papers to prevent bleeding of recording liquid and to improve image fastness, especially for color recording to maintain or improve color properties and color tones. Regarding the recording liquid, mainly the quick-drying property of the recording liquid, the fastness of the dye contained in the recording liquid, the print density of the printed matter printed on the paper by the recording liquid, the sticking of the recording apparatus, the one-shot property, etc. Many things have been done, such as research on improving the reliability of. It is possible to perform good recording on plain paper such as copy paper, letter paper, foam paper, notebook, notepaper, and recycled paper recycled from these papers, which have recently become popular in offices and homes. As possible, detailed research and development have been conducted from various aspects regarding the composition and physical properties of the recording liquid. That is, the main ones of these studies include improvement of the density of the printed image, feathering, or discoloration (bronze phenomenon) of the printed material when the surface pH of the recording material is low (acidic paper). To be Also, the robustness of the printed image is improved,
There are many things related to the improvement of reliability such as sticking of the recording apparatus and the one-shot property. In particular, many studies have been conducted on the water resistance of the recording liquid of printed matter, even among the fastnesses. In general, since an aqueous recording liquid is used for liquid jet recording, when recording is performed using such a recording liquid, since the coloring material used in the ink is a water-soluble dye, sweat and This is because there is a problem that the printed image bleeds due to water drops or the like, and the image becomes unclear or damaged.

[0003]

[Problems to be Solved by the Invention]

(First to Fourth Inventions) However, in any of the printed images on the coated paper, plain paper, recycled paper, etc. in the above-mentioned conventional example, the color tone and gloss of the printed matter are soft and close to human skin, and However, there has been no recording liquid for a liquid jet recording device, which has a moisturizing feel to the printed matter and exhibits an effect similar to that of bare skin. Therefore, an object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a printed matter having excellent characteristics in any printed image printed on coated paper, plain paper, recycled paper, and the like. It is an object of the present invention to provide a possible recording liquid, a liquid jet recording method using the recording liquid, and an apparatus using the recording liquid.

(Fifth Invention) Further, in a recording apparatus using a recording liquid, it is general to replace the cartridge containing the recording liquid to replenish the recording liquid, and particularly in the case of a liquid jet recording apparatus. If air bubbles in the recording liquid cause non-ejection of the recording liquid, put a bag with more airtightness inside the cartridge, and use the recording liquid bag containing the recording liquid in it. Is commonly done. The recording liquid bag accommodated in these ink cartridges becomes a waste after the recording liquid in the bag is completed, and is generally incinerated. However, all the conventional materials for forming the recording liquid bag have a problem that when they are discarded as waste, they generate a large amount of heat or cause environmental pollution. Therefore, another object of the present invention is to store the excellent recording liquid of the present invention as described above and to use it in the above-mentioned recording apparatus and the like, especially when it is discarded or incinerated, the treatment is easy and the environment An object of the present invention is to provide an ink cartridge having a recording liquid bag in which the occurrence of contamination is extremely small.

[0005]

The above object can be achieved by the present invention described below. That is, the first invention is a recording liquid containing a dispersion liquid in which a water-insoluble protein is dispersed with a water-soluble protein, and the second invention is a recording liquid containing 0.1% or more of a water-soluble protein. The third invention is a liquid jet recording method using these, the fourth invention is a device using these recording liquids, and the fifth invention is An ink cartridge having a recording liquid bag made of amorphous polyethylene terephthalate.

[0006]

[Action]

(First to Fourth Inventions) As a result of earnest research to solve the above-mentioned problems of the prior art, the present inventors have found that the recording liquid contains proteins,
In particular, by containing a protein that constitutes a living body, a printed image formed by such a recording liquid has a color tone and gloss close to that of human skin and a soft touch and close to that of bare skin. The present invention has been completed by finding that it is possible to give a high-grade feeling. Further, in particular, when the recording liquid of the present invention is used when the recording method is a system in which the liquid is ejected by the heat generated from the heating element, the water-soluble protein contained in the recording liquid is solidified by the high heat generated during printing, Since the film is formed on the recording material, the water resistance of the printed image is also improved. Since the above-mentioned film is formed by denaturing the protein, it has little redissolvability in an aqueous solution and the water resistance of the printed image is improved. Further, these things simultaneously suppress the permeation of the recording liquid into the recording material, and the density of the printed image becomes high because a large number of coloring materials in the recording liquid exist on the surface of the recording material. Further, since the penetrant is suppressed by such a phenomenon, feathering in which the recording liquid is adsorbed along the fibers on the recording material and blurring of the edge of the printed image are reduced. Therefore, the printing quality is improved as compared with the conventional case. Especially, the copy that is widely used in offices and homes,
The effect of each paper such as form or letter, notebook, notepaper, continuous slip paper, etc., and uncoated paper (plain paper) such as recycled paper created by recycling of these papers is dramatically higher than before. improves. Furthermore, many proteins have hygroscopicity, and the use of such proteins enhances the wettability of the ink ejection portion in the liquid ejecting recording apparatus, thus preventing clogging of the protrusions such as pigments. It can be improved over the long term.

(Fifth Invention) Further, as a result of earnest research to solve the above-mentioned problems in containing the recording liquid, the present inventors have used amorphous polyethylene terephthalate (A-PET) as a material for the bag. For example, A-PET
Maintains the excellent properties of conventional polyethylene terephthalate (PET) such as chemical resistance, gas barrier properties and transparency, and is more flexible than PET and has a smaller calorific value in combustion than conventional plastics. Further, the present invention has been completed by finding that it has a characteristic that no harmful gas such as hydrogen chloride is generated, and therefore the problems of the above-mentioned conventional techniques can be solved. That is, the ink cartridge of the present invention having a bag formed of A-PET has very little environmental pollution unlike the conventional recording liquid bag, and further, A-PET
Has excellent transparency, gas barrier property, and chemical resistance, so that A-PET can be used alone to form a bag without using a multi-layered structure unlike the recording liquid bag used conventionally.
Therefore, it becomes possible to visually detect the remaining amount of the recording liquid,
Since the film has good moldability, it is possible to provide a film that is cheaper and has less environmental pollution than the conventional recording liquid bag.

[0008]

[Preferred Embodiment]

(First and Second Inventions) Next, the present invention will be described in detail with reference to preferred embodiments. A first invention of the present invention is a recording liquid containing a dispersion liquid in which a water-insoluble protein is dispersed with a water-soluble protein. In particular, when a recording liquid contains a protein constituting a living body, the printed image formed by the recording liquid of the present invention has a color tone,
The gloss is close to that of human skin, and the touch is soft and close to that of bare skin, and these effects give the printed image a high-quality appearance.
In addition, the second invention of the present invention provides a water-soluble protein of 0.
A recording liquid containing 1% or more.

The water-insoluble protein used in the recording liquid of the present invention is a protein having a large amount of water-insoluble matter. Specifically, simple proteins such as prolamin, glutelin and histone, keratin, fibroin, resilin, Fibrinogen, fibrin proteins such as fibrin, deoxyribonucleoproteins and ribonucleoproteins, pigment proteins, phosphoproteins and the like, but fibrous proteins that are components of the skin are preferable, among them,
Keratin, fibroin, resilin, fibrinogen and fibrin, which are poorly water-soluble, are more preferable. Further, since the ejection port of the liquid ejecting apparatus is small, it is preferable that the particle size of these proteins to be used is smaller, generally 200 μm or less, and more preferably 100 μm or less. Further, the water-soluble protein used in the recording liquid of the present invention is mainly a protein having a high water-soluble content among proteins, and specifically, simple proteins such as albumin and globulin, fibers such as collagen and elastin, etc. Protein, glycoproteins contained in various organs and cell membranes, inducible proteins such as gelatin, proteose and peptone, and derivatives thereof. Of these, fibrous proteins and their derivatives that constitute the skin are preferable, and among the fibrous proteins, collagen and elastin, which have a high water-soluble content, are more preferable.

The dispersion liquid used in the recording liquid of the present invention contains the above water-insoluble protein as a water-soluble protein,
Preferably 10: 1 to 1: 1 and more preferably 5: 1 to
It is dispersed at a ratio of 2: 1. That is, when the ratio of the water-insoluble protein to the water-soluble protein in the dispersion liquid contained in the recording liquid is closer than 10: 1, the dispersion stability is poor and the water-insoluble protein precipitates upon storage. If such sedimentation occurs in the ink cartridge, the human skin feel of the image is lost, and it may cause clogging of the ink supply tube, the nozzle, the ejection port, and the like, which is not preferable. Further, when the ratio is 1: 1 or more, the dispersion stability is extremely good, but since the viscosity increases, the order of the ink during printing is deteriorated, which is not preferable.

The dispersion liquid as described above is contained in the recording liquid of the present invention in an amount of 0.1% or more in terms of solid content, more preferably 0.1.
5-10% included. That is, when the solid content concentration of these dispersions is less than 0.1%, the effect on human skin is diminished, which is not preferable. On the other hand, if the solid content concentration exceeds 10%, the viscosity of the recording liquid increases, which deteriorates the order, and the denatured protein causes clogging of the nozzles and deterioration of the heating element due to adhesion to the heating element. , Not preferable.

The pH of the recording liquid of the present invention prevents denaturation and alteration of proteins contained in the recording liquid, and elutes the peripheral member of the recording liquid (member in contact with the recording liquid) into the recording liquid. To prevent this, adjust the pH from weakly acidic to weakly alkaline (pH = 4.0-1
0), more preferably around neutral.

The liquid medium used in the recording liquid of the present invention is a mixture of water and a water-soluble organic solvent. As water, in addition to ordinary water, deionized water is preferably used. Examples of the organic solvent used at this time include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-
Butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-pentanol and the like having 1 to 5 carbon atoms
Alkyl alcohols or halogenated derivatives thereof; amides such as dimethylformamide and dimethylacetamide; ketones or keto alcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; diethylene glycol, triethylene glycol, tetraethylene Oxyethylene or oxypropylene addition polymers such as glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, polypropylene glycol; ethylene glycol, propylene glycol, trimethylene glycol, butylene glycol, 1,2,6-hexanetriol, hexylene. 2-6 alkylene groups such as glycol
Alkylene glycols containing 1 carbon atom; thiodiglycol; glycerin; ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monomethyl (or ethyl) ether, and other lower polyhydric alcohols Alkyl ethers; lower dialkyl ethers of polyhydric alcohols such as triethylene glycol dimethyl (or ethyl) ether and tetraethylene glycol dimethyl (or ethyl) ether; sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone and the like can be mentioned. The content of the water-soluble organic solvent is generally in the range of 2% to 50% by weight, preferably 2% to 30%, based on the total weight of the recording liquid. The above media can be used alone or as a mixture.

The dyes used in the recording liquid of the present invention include direct dyes, acid dyes, food dyes, basic dyes, reactive dyes, disperse dyes, vat dyes, soluble vat dyes, reactive disperse dyes, oil dyes. And other dyes, and various pigments.
The content of these dyes is determined depending on the kind of the liquid medium component, the characteristics required for the recording liquid, etc., but is generally about 0.2 to 20% by weight in the total amount of the recording liquid. It is preferably 0.5 to 10%, more preferably 1 to 5%.

The main components of the recording liquid of the present invention are as described above, but other various dispersants, surfactants, viscosity modifiers,
A surface tension adjusting agent, a fluorescent whitening agent and the like can be added as necessary within a range not hindering the achievement of the object of the present invention. For example, viscosity adjusting agents such as polyvinyl alcohol, celluloses and water-soluble resins; surface tension adjusting agents such as various cationic, anionic or nonionic surfactants, diethanolamine and triethanolamine;
H regulators; antifungal agents and the like can be mentioned.

When a recording liquid used in a liquid jet recording method of charging the recording liquid is prepared, a specific resistance adjusting agent such as an inorganic salt such as lithium chloride, ammonium chloride or sodium chloride is added. It The recording liquid of the present invention is particularly suitable when applied to a liquid jet recording method of the type in which the recording liquid is ejected due to the bubbling phenomenon of the recording liquid due to thermal energy, the ejection becomes extremely stable, and the occurrence of satellite dots, etc. There is a feature that does not occur. However, in this case, thermal physical property values (for example, specific heat, thermal expansion coefficient, thermal conductivity, etc.) may be adjusted. Furthermore, the recording liquid of the present invention can be used to solve the problems of bleeding of the recording liquid and the drying and penetrating properties of the recording liquid when recording on plain paper, and at the same time improve the matching with the liquid jet head. As the physical properties of the liquid itself, it is desirable to adjust the surface tension at 25 ° C. to 30 to 68 dyne / cm and the viscosity to 15 cP or less, preferably 10 cP or less, and more preferably 5 cP or less. Therefore, in order to adjust the recording liquid to the above physical properties and solve the problem of plain paper, the amount of water contained in the recording liquid of the present invention is 50% by weight or more,
More preferably, the amount is 60% by weight or more.

(Third and Fourth Inventions) The recording liquid of the present invention described above is particularly suitable for use in a liquid jet recording method in which droplets are ejected by the action of thermal energy for recording. It goes without saying that it can also be used for business. As a method and an apparatus suitable for performing recording using the recording liquid of the present invention, thermal energy corresponding to a recording signal is applied to the recording liquid in the chamber of the recording head,
Examples include a method and an apparatus for generating droplets by the thermal energy.

An example of the head structure, which is the main part of the apparatus, is shown in FIGS. 1, 2 and 3. The head 13 is made of glass, ceramics, a plastic plate or the like having a groove 14 for passing a recording liquid, and a heating head 15 (a head is shown in the drawing, but not limited to this) used for thermal recording. Obtained by gluing. The heating head 15 includes a protective film 16 made of silicon oxide and an aluminum electrode 17.
1, 17-2, a heat-generating low antibody layer 18 formed of nichrome, a heat storage layer 19, and a substrate 20 having a good heat dissipation property such as alumina.
Has become The recording liquid 21 reaches the discharge orifice (fine hole) 22 and forms a meniscus 23 by the pressure P. Now, when an electric signal is applied to the electrodes 17-1 and 17-2, the area indicated by n of the heating head 15 rapidly generates heat, and bubbles are generated in the recording liquid 21 in contact with the area, and the meniscus is generated by the pressure. The recording liquid 21 is ejected from the nozzle 23, and the recording liquid 21 is ejected to form a recording droplet 24 from the orifice 22 and fly toward the recording material 25. FIG. 3 shows an external view of a multi-head in which many heads shown in FIG. 1 are arranged. The multi-head is manufactured by closely contacting a glass plate 27 having a multi-groove 26 and a heating head 28 similar to that described in FIG. Incidentally, FIG. 1 shows the head 13 along the recording liquid flow path.
2 is a cross-sectional view of FIG. 2, and FIG. 2 is a cross-sectional view taken along the line AB of FIG.

FIG. 4 shows an example of a liquid jet recording apparatus incorporating such a head. In FIG. 4, reference numeral 61 denotes a blade as a wiping member, one end of which is held by a blade holding member to become a fixed end, which is in the form of a cantilever. The blade 61 is arranged at a position adjacent to the recording area of the recording head, and in the case of this example, is held in a protruding form in the moving path of the recording head. 62
Is a cap, which is arranged at a home position adjacent to the blade 61, and has a configuration for moving in a direction perpendicular to the moving direction of the recording head to come into contact with the ejection port surface for capping. Further, 63 is a recording liquid absorber provided adjacent to the blade 61, and like the blade 61, is held in a protruding form in the moving path of the recording head. The blade 61, the cap 62, and the absorber 63 constitute an ejection recovery unit 64, and the blade 61 and the absorber 63 remove water, dust, and the like from the recording liquid ejection port surface.

Reference numeral 65 denotes a recording head which has a discharge energy generating means and discharges a recording liquid to a recording material facing the discharge port surface where the discharge ports are arranged to perform recording. A carriage for moving the head 65. The carriage 66 is slidably engaged with the guide shaft 67, and a part of the carriage 66 is connected (not shown) to a belt 69 driven by a motor 68. As a result, the carriage 66 can move along the guide shaft 67, and the recording head 65 can move the recording area and its adjacent area. Reference numeral 51 is a paper feed section for inserting a recording material, and 52 is a paper feed roller driven by a motor (not shown). With these configurations, the recording material is fed to a position facing the ejection port surface of the recording head, and is ejected to a paper ejection unit provided with a paper ejection roller 53 as the recording progresses.

In the above structure, when the recording head 65 returns to the home position after recording is completed, the cap 62 of the head recovery section 64 is retracted from the movement path of the recording head 65, but the blade 61 is projected into the movement path. There is. As a result, the ejection port surface of the recording head 65 is wiped. When the cap 62 comes into contact with the ejection surface of the recording head 65 to perform capping, the cap 62 moves so as to project into the movement path of the recording head. Recording head 6
When 5 moves from the home position to the recording start position, the cap 62 and the blade 61 are at the same position as the above-described position at the time of wiping. As a result, the ejection opening surface of the recording head 65 is wiped even during this movement. To move the recording head to the home position,
Not only at the end of recording or at the time of ejection recovery, the recording head moves to the home position adjacent to the recording area at a predetermined interval while moving in the recording area for recording, and the wiping is performed with this movement. .

FIG. 5 is a diagram showing an example of a recording liquid cartridge in which the recording liquid is supplied to the head via a recording liquid supply member, for example, a tube. Reference numeral 40 denotes a recording liquid container, for example, a recording liquid bag, which stores the recording liquid for supply, and a rubber stopper 42 is provided at the tip thereof. By inserting a needle (not shown) into this stopper 42, the recording liquid in the recording liquid bag 40 can be supplied to the head. 44
Is a recording liquid absorber that receives the waste recording liquid. It is preferable for the present invention that the liquid contact surface of the recording liquid accommodating portion is made of polyolefin, especially polyethylene. The liquid jet recording apparatus used in the present invention is not limited to the one in which the head and the recording liquid cartridge are separate as described above, but is also suitably used in the one in which they are integrated as shown in FIG. To be

In FIG. 6, reference numeral 70 denotes a recording unit, in which a recording liquid containing portion for containing a recording liquid, for example, a recording liquid absorber is contained, and the recording liquid in the recording liquid absorber is contained. Head portion 71 having a plurality of orifices
It is configured to be ejected as recording droplets from the. For the present invention, it is preferable to use polyurethane as the material of the recording liquid absorber. Reference numeral 72 denotes an atmosphere communication port for communicating the inside of the cartridge with the atmosphere. The recording unit 70 is used in place of the recording head shown in FIG. 4, and is detachable from the carriage 66.

(Fifth Invention) In the recording apparatus using the recording liquid as described above, it is common to replace the cartridge containing the recording liquid to replenish the recording liquid, and in particular,
If air bubbles in the recording liquid cause the recording liquid not to be ejected as in the liquid jet recording device as described above, put a more airtight bag in the cartridge and put the recording liquid in it. It is common practice to store the enclosed recording liquid bag. By the way, these recording liquid bags become waste at the end of the recording liquid and are generally incinerated. Conventionally, as a constituent material of such a recording liquid bag, various plastic films, metal foils and the like have been generally used individually or in a laminate. Specific examples of the plastic film include polyethylene, polyamide, polypropylene, polyethylene terephthalate, polyvinyl chloride, and polyvinylidene chloride. However, when a bag made of these materials is incinerated after being used, and when it is formed of polyethylene, polyamide, polypropylene, or polyethylene terephthalate, they all generate more heat than wood and paper (about 2.5 times) There is a problem of shortening the life of the incinerator,
In the case of polyvinyl chloride and polyvinylidene chloride, although the calorific value is equivalent to that of wood and paper, there is a problem that hydrogen chloride is generated during incineration, which causes environmental pollution. Further, since many of these materials have poor gas barrier properties, it has been general to use them by laminating a metal foil or the like as described above. Therefore, there is a problem that the recording liquid bag becomes opaque and the remaining amount of the recording liquid cannot be easily detected visually.

[0025] Conventionally, when incinerated, there is no incineration residual soil, a calorific value similar to that of wood and no harmful gas is generated, and recovery and regeneration are attempted. There was no ink cartridge having a recording liquid bag with little contamination. As a result of earnest research to solve the problems of the prior art, the inventors of the present invention can solve the above problems by using amorphous polyethylene terephthalate (A-PET) as a material forming the recording liquid bag. The present invention has been completed by finding out what can be done. That is, A-PET is PET while maintaining excellent properties such as chemical resistance, gas barrier property, and transparency that conventional polyethylene terephthalate (PET) has.
It is more flexible than, has the same calorific value in combustion as wood, is smaller than conventional plastics, and
No harmful gas such as hydrogen chloride is generated when incinerated. Furthermore, polyethylene terephthalate is a material that is currently being collected and recycled (recycled).
Like ET, ET can be recycled.
As described above, the recording liquid bag made of A-PET has very little environmental pollution unlike the conventional bag. Furthermore, since A-PET is excellent in both transparency and gas barrier property, A-PET does not have a multi-layer structure like the conventional recording liquid bag,
-PET alone can form a bag. Therefore, it is possible to visually detect the remaining amount of the recording liquid, and since the film formability is good, compared to the conventional recording liquid bag,
It is possible to provide a bag that is inexpensive and has little environmental pollution when incinerated.

[0026]

EXAMPLES The present invention will be described in more detail with reference to the following preferred examples and comparative examples. The parts and% are based on weight unless otherwise specified. Recording solutions of Examples 1 to 5 of the present invention and Comparative Examples 1 to 4 were obtained using the compositions shown below.

Example 1 Dispersion A 5 parts (solid content 0.6%) Diethylene glycol 10 parts Food Black 2 3 parts Pure water 82 parts

Example 2 Dispersion B 66 parts (solid content 9.9%) Diethylene glycol 10 parts Food black 2 3 parts Pure water 21 parts

Example 3 Dispersion B 20 parts (solid content 3.0%) Diethylene glycol 10 parts Food Black 2 3 parts Pure water 72 parts

Example 4 Dispersion C 50 parts (solid content 6.0%) Diethylene glycol 10 parts Food Black 2 3 parts Pure water 47 parts

Example 5 Dispersion C 40 parts (solid content 3.8%) Diethylene glycol 10 parts Food Black 2 3 parts Monoethanolamine 0.5 parts Pure water 56.5 parts

Comparative Example 1 Dispersion B 80 parts (solid content 12%) Diethylene glycol 10 parts Food black 3 parts Pure water 7 parts

Comparative Example 2 Dispersion A 3 parts (solid content 0.36%) Diethylene glycol 10 parts Food Black 3 parts Pure water 74 parts

Comparative Example 3 Dispersion D 20 parts (solid content 2.2%) Diethylene glycol 10 parts Food Black 2 3 parts Pure water 67 parts

Comparative Example 4 Dispersion E 0.5 part (solid content 0.8%) Diethylene glycol 10 parts Food Black 2 3 parts Pure water 86.5 parts

As the dispersions A to E described above, the dispersions having the compositions shown in Table 1 below were used and dispersed by a homogenizer (manufactured by Nippon Seiki Co., Ltd.) to prepare respective dispersions. As the dispersion conditions at this time, the dispersion time was 60 minutes, and the rotation speed was 5000 rpm.

[0037]

[Table 1]

Recording solutions of Examples 6 to 10 of the present invention and Comparative Examples 5 to 7 were obtained using the compositions shown below. Example 6 α2-elastin (bovine cervical ligament) (elastin product) 0.5 part Diethylene glycol 10 parts Food Black 2 3 parts Pure water 86.5 parts

Example 7 β-elastin (bovine cervical ligament) (manufactured by Funayoshi Chemical Co., Ltd.) 10 parts Diethylene glycol 10 parts Food Eosin 3 parts Pure water 77 parts

Example 8 k-elastin (bovine cervical ligament) (elastin product) 3 parts Diethylene glycol 10 parts Food grade quinoline 3 parts Pure water 84 parts

Example 9 α-elastin (bovine cervical ligament) (elastin product) 5 parts ・ diethylene glycol 20 parts ・ ethanol 3 parts ・ carbon black aqueous dispersion A 30 parts ・ pure water 42 parts

Example 10 β-elastin (bovine cervical ligament) (elastin product) 5 parts Diethylene glycol 20 parts Ethanol 3 parts Carbon black aqueous dispersion B 30 parts Pure water 42 parts

The above-mentioned carbon black aqueous dispersions A and B were prepared by dissolving the resin having the following composition in water using a neutralizing agent, monoethanolamine, and then using a sand grinder (Igarashi Machinery Co., Ltd.). Each dispersion was prepared by using The dispersion conditions at this time were a dispersion time of 4 hours and a rotation speed of 15,000 rpm.・ Carbon black aqueous dispersion A Carbon black (Mitsubishi Kasei MCF88) 10 parts Styrene maleic acid (manufactured by Starlight Chemical Co., molecular weight 15000, acid value 180) 2 parts ・ Carbon black aqueous dispersion B carbon black (Degussa S170) 10 parts Styrene maleic acid ( Hoshiko Chemical, molecular weight 12000, acid value 140) 3 parts

Comparative Example 5-Elastin 0.1 part as in Example 6-Diethylene glycol 10 parts-Food Black 2 3 parts-Pure water 86.9 parts

Comparative Example 6-Elastin 11 parts as in Example 6-Diethylene glycol 10 parts-Food Black 2 3 parts-Pure water 76 parts

Comparative Example 7 Diethylene glycol 10 parts Food Black 2 3 parts Pure water 87 parts

Example of Use Next, using the respective recording liquids prepared in Examples 1 to 10 and Comparative Examples 1 to 7, thermal energy is applied to the recording liquid in the recording head to generate droplets, Solid printing was performed by a printing apparatus (bubble jet printer BJ-10V, manufactured by Canon Inc.) having an on-demand type multi-head for printing, and a print piece of 10 × 20 mm was prepared. Canon NP-6150 can be used for printing paper
Recommended paper for use, Neusiedler paper (abbreviated as ND) and prober bond paper (abbreviated as PB) were used.

Evaluation The optical density of the resulting print was measured,
As shown in Table 2, the optical density of any printed matter is 1.30.
Was in the range of ˜1.50. Further, the printed piece was immersed in still water at 20 ° C. for 3 hours, and then the reduction rate of optical density was measured to evaluate the water resistance of the printed matter.
All the printed materials using the recording liquids of Examples 1 to 10 had an optical density reduction rate of 15% or less, and showed excellent water resistance. On the other hand, as shown in Table 3, the recording liquids of Comparative Examples were inferior in water resistance.

Further, in order to evaluate the human skin sensation of the obtained printed matter, a visual test and a tentacle test were evaluated by the following methods and criteria, and the results are shown in Tables 2 and 3. Visual test Visual tests were conducted by 20 people, 10 each for men and women, and judged according to the following criteria. 3 points: eyes to the easy two points: Traditional different from those one point: do conventional and tentacles test tentacles test that does not change the men and women in each of the 10 people a total of 20 people, was judged by the following criteria. 3 points: Soft feeling 2 points: Different from the conventional one Point: No change from the conventional result As a result, both the visual test and the tentacle test of each printed matter are shown in Table 2 as in any of the examples. But 53-60
Got the points score. On the other hand, in the recording liquid of the comparative example, Table 3
As shown in Fig. 3, the human skin was inferior in feeling.

[0050]

[Table 2] Table 2 Evaluation results

[0051]

[Table 3] Continuation of Table 2 Evaluation results

[0052]

[Table 4] Table 3 Evaluation results

Further, the obtained printed matter was evaluated for discharge stability, storability and clogging recovery by the following methods and criteria, and the results are shown in Tables 4 and 5. The pH of each recording liquid was measured with a pH meter, and the results are also shown.

Storability As for the storability, whether or not it is possible to print until the ink is used up by leaving an ink cartridge filled with a predetermined ink for 3 months under the conditions of normal temperature and normal humidity (25 ° C., 60%). Was used as the criterion.

[0055] As the clogging recoverability clogging recovery property test, filling the predetermined ink into the ink cartridge, after the continuous printing 5 minutes using the same printer as described above, the ink cartridge was capped Without, 1 at room temperature of 25 ℃, 60%
After leaving for 0 days, reprinting was performed, and the recovery state at this time was observed and evaluated according to the following criteria. ◯: Normal printing is possible with 1-3 recovery operations. X: Recovery operation of 4 times or more is required. Table 4 shows the results of evaluation of the inks of Examples and Comparative Examples based on the above criteria.

[0056]

[Table 5] Table 4 Evaluation results

Examples 11 to 14 and Comparative Examples 8 to 9 The recording liquid bags of Examples 11 to 14 and Comparative Examples 8 to 9 were formed with the materials and molding methods shown in Table 5, respectively.

[0058]

[Table 6] Table 5 Materials for the recording liquid bag

Each of the bags formed as described above was filled with the recording liquid of the present invention and contained, and the bag containing the recording liquid was loaded into the ink cartridge and recorded by the liquid jet recording apparatus. It was possible to smoothly supply the recording liquid. In addition, the characteristics of these bags and the characteristics during incineration after use were evaluated for the following items based on the following criteria. The results are shown in Table 6.

Evaluation Calorific Value The calorific value upon incineration was measured using a cylinder calorimeter.

[0061] generation of hydrogen chloride upon generation amount incineration of the hydrogen chloride content of JIS K-72
28.

Gas barrier property Oxygen permeability was measured based on JIS K-7126 and evaluated according to the following criteria. ○: <0.50 cc · mm / cm ² · sec · cm
Hg · 10 ¹⁰ Δ: < ² cc · mm / cm ² · sec · cmHg ·
10 ¹⁰ ×: 2 ≦ cc · mm / cm ² · sec · cmHg ·
10 ¹⁰

A recording liquid was poured into a transparent recording liquid bag, and whether or not the remaining amount of the recording liquid could be visually confirmed was used as an evaluation criterion.

[0064]

[Table 7] Table 6 Evaluation results

[0065]

【The invention's effect】

(First to Fourth Inventions) As described above, the recording liquid of the present invention contains a protein, particularly a water-soluble protein, in the recording liquid, so that the color tone and gloss of the printed image are softer than the conventional ones. Becomes In addition, there is a moisturizing sensation, which gives a human skin sensation. These features give the image a high quality look. Furthermore,
The protein is denatured by light heat from the heating element during printing, forming a film on the recording material. Since the film formed by this modification is insoluble in water, even if sweat, water droplets, etc. adhere to the printed image, bleeding or bleeding due to redissolution of the color former in water does not occur. Therefore, the water resistance of the printed image using these recording liquids is extremely good. Further, since the above-described phenomenon suppresses the immersion of the recording liquid in the recording material, the density of the printed image is increased, and feathering and blurring around the dots are eliminated. Therefore, when the recording liquid of the present invention is printed using this, not only coated paper but also so-called non-coated paper such as copy, letter, form, etc., which is widely used, has a dramatically improved image quality compared to the conventional one. improves. Further, the hygroscopicity, which is a characteristic of the fiber protein, keeps the recording liquid ejection surface of the liquid ejecting apparatus wet, so that non-ejection due to clogging does not occur for a long period of time as compared with the conventional case.

(Fifth Invention) Further, as described above, the ink cartridge of the present invention can supply the recording liquid to the recording means smoothly, and of course, the recording liquid contained in the ink cartridge. The bag has little environmental pollution when it is incinerated after use, and the recording liquid bag can be collected and regenerated, and the remaining amount can be visually detected, which is excellent in environmental protection and economy. It is a thing.

[Brief description of drawings]

FIG. 1 is a vertical sectional view of a head portion of a liquid jet recording apparatus.

FIG. 2 is a cross-sectional view of a head portion of a liquid jet recording apparatus.

3 is an external perspective view of a head in which the head shown in FIG.

FIG. 4 is a perspective view showing an example of a liquid jet recording apparatus.

FIG. 5 is a vertical sectional view of an ink cartridge.

FIG. 6 is a perspective view of a recording unit.

FIG. 7 shows a recording liquid bag accommodated in the ink cartridge of the present invention, (a) is a schematic plan view, and (b) is A-.
It is sectional drawing of an A'direction.

[Explanation of symbols]

 61: Wiping member 62: Cap 63: Recording liquid absorber 64: Ejection recovery section 65: Recording head 66: Carriage 1: Recording liquid bag body 2: Recording liquid supply tube 3: Ink

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location B41M 5/00 E 9221-2H C09D 11/04 PTJ 7415-4J

Claims (16)

[Claims] 1. A recording liquid comprising a dispersion liquid in which a water-insoluble protein is dispersed with a water-soluble protein. 2. The recording liquid according to claim 1, wherein the dispersion liquid comprises a water-insoluble protein and a water-soluble protein dispersed at a ratio of 10: 1 to 1: 1. 3. The recording liquid according to claim 1, which contains 0.1% or more of the dispersion liquid in terms of solid content. 4. A recording liquid containing 0.1% or more of a water-soluble protein. 5. The recording liquid according to claim 1, which contains a fibrous protein and / or a derivative thereof as the protein. 6. The recording liquid according to claim 1, wherein the pH of the recording liquid is in the range of 4.0 to 10. 7. A recording method for recording on a recording material by ejecting a recording liquid from an orifice according to a recording signal,
A liquid jet recording method, wherein the recording liquid is the recording liquid according to claim 1 or 4. 8. The liquid jet recording method according to claim 7, wherein thermal energy is applied to the recording liquid to eject recording liquid droplets. 9. A recording liquid containing a recording liquid and a recording unit having a head portion for ejecting the recording liquid as recording liquid droplets, wherein the recording liquid is the recording liquid according to claim 1 or 4. A recording unit characterized in that. 10. The head unit is a head for ejecting recording liquid droplets by causing thermal energy to act on the recording liquid.
Recording unit described in. 11. A liquid jet recording apparatus, comprising: a recording liquid containing portion containing a recording liquid; and a recording unit having a head portion for ejecting the recording liquid as recording liquid droplets. A liquid jet recording apparatus, which is the recording unit described in 1. 12. The liquid jet recording apparatus according to claim 11, wherein the head portion is a head that applies thermal energy to the recording liquid to eject the thermal energy. 13. An ink cartridge provided with a recording liquid storage unit for storing a recording liquid, wherein the recording liquid is the recording liquid according to claim 1 or 4. 14. An ink cartridge comprising a recording liquid bag made of amorphous polyethylene terephthalate for containing a recording liquid. 15. A recording head for ejecting a recording liquid, an ink cartridge having a recording liquid containing portion containing the recording liquid, and a recording liquid supply portion for supplying the recording liquid from the ink cartridge to the recording head. A liquid jet recording apparatus, wherein the ink cartridge is the ink cartridge according to claim 13 or 14. 16. The recording head is a head for causing thermal energy to act on a recording liquid and ejecting the thermal energy.
The liquid jet recording apparatus according to item 1.