Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
  • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
  • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
  • B41J2/01—Ink jet
  • B41J2/135—Nozzles
  • B41J2/165—Preventing or detecting of nozzle clogging, e.g. cleaning, capping or moistening for nozzles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
  • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
  • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
  • B41J2/01—Ink jet
  • B41J2/135—Nozzles
  • B41J2/165—Preventing or detecting of nozzle clogging, e.g. cleaning, capping or moistening for nozzles
  • B41J2/16505—Caps, spittoons or covers for cleaning or preventing drying out
  • B41J2/16508—Caps, spittoons or covers for cleaning or preventing drying out connected with the printer frame
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
  • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
  • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
  • B41J2/01—Ink jet
  • B41J2/135—Nozzles
  • B41J2/165—Preventing or detecting of nozzle clogging, e.g. cleaning, capping or moistening for nozzles
  • B41J2/16517—Cleaning of print head nozzles
  • B41J2/1652—Cleaning of print head nozzles by driving a fluid through the nozzles to the outside thereof, e.g. by applying pressure to the inside or vacuum at the outside of the print head
  • B41J2/16523—Waste ink collection from caps or spittoons, e.g. by suction
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
  • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
  • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
  • B41J2/01—Ink jet
  • B41J2/17—Ink jet characterised by ink handling
  • B41J2/175—Ink supply systems ; Circuit parts therefor
  • B41J2/17503—Ink cartridges
  • B41J2/17513—Inner structure
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
  • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
  • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
  • B41J2/01—Ink jet
  • B41J2/17—Ink jet characterised by ink handling
  • B41J2/175—Ink supply systems ; Circuit parts therefor
  • B41J2/17503—Ink cartridges
  • B41J2/1752—Mounting within the printer
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
  • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
  • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
  • B41J2/01—Ink jet
  • B41J2/17—Ink jet characterised by ink handling
  • B41J2/175—Ink supply systems ; Circuit parts therefor
  • B41J2/17503—Ink cartridges
  • B41J2/17553—Outer structure
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
  • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
  • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
  • B41J2/01—Ink jet
  • B41J2/21—Ink jet for multi-colour printing
  • B41J2/2107—Ink jet for multi-colour printing characterised by the ink properties
  • B41J2/2114—Ejecting transparent or white coloured liquids, e.g. processing liquids
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/32—Inkjet printing inks characterised by colouring agents
  • C09D11/322—Pigment inks

Definitions

• the present invention relates to a pigment ink, an ink set, an ink jet recording method, an ink
• the present invention relates to a cartridge, a recording unit, an ink jet recording apparatus, and an image forming method. ',
• the ink jet recording method is a method of recording an image by ejecting ink onto a recording medium, and does not require a complicated device, so that the running cost can be kept low, and the ink jet recording device can be reduced in size and color. Easy. For this reason, various recording apparatuses such as printers, copiers, facsimile machines, word processors, and the like using the inkjet recording method have been widely used. In such an ink jet recording technique, it is possible to form a multicolor image using black ink and coloring (for example, yellow ink, cyan ink, magenta ink, red ink, green ink and blue ink). It has been broken. Among them, the black ink uses an ink containing a pigment as a coloring material for the purpose of improving the image density and the character quality (Japanese Patent Laid-Open No. 2000-019-98). 9 5 5).
• a typical solution is that, when a plurality of inks having different hues are applied to a recording medium adjacent to each other, at least one kind of ink is increased in viscosity, or color material aggregation or 3 ⁇ 4t. This is a method that suppresses the occurrence of bleeding.
• anionic ink and cationic ink one of these inks contains a polymer having the same ionicity as the ink.
• a method of applying these inks to a recording medium so as to be in contact with each other is disclosed (see Japanese Patent No. 2 898 8 17).
• first ink and the second ink containing a precipitating agent that reacts with the coloring material in the first ink to form a precipitate, so that these inks are in contact with each other.
• a polyvalent metal is used for the precipitant.
• Image quality has been improved by the technology for obtaining excellent bleeding resistance as described above.
• the emphasis is on how to react ink efficiently, that is, how to improve ink reactivity in order to obtain excellent pre-proofing resistance. In some cases, sufficient reliability could not be obtained. Therefore, in order to solve the above-described problems, it has been widely practiced to cap discharge ports for discharging a plurality of inks that react with each other with a plurality of caps.
• the use of a plurality of caps as described above has resulted in an increase in the size of the ink jet recording apparatus, a complicated mechanism, and an increase in cost.
• the present inventors have studied to achieve both reliability, miniaturization of the ink jet recording apparatus, simplification of the mechanism, and cost reduction.
• the study was carried out to cover the pigment ink discharge port and the ink discharge port that reacts with the pigment ink by using the same cap (cap for exclusive use when left).
• the high level of reliability required in recent years cannot be sufficiently obtained by using the above-described configuration, that is, by simply performing T-cabbing using the same cap for the ejection ports of a plurality of inks that react with each other. I understood.
• a plurality of inks that react with each other come into contact with each other to generate aggregates, and the aggregates adhere to the recording head, thereby deteriorating reliability. I found out.
• a first object of the present invention is to provide bleeding resistance for use in an ink jet recording apparatus in which a pigment ink discharge port and a ink discharge port that reacts with the pigment ink are capped with the same cap.
• the object is to provide pigment inks that are both reliable.
• a second object of the present invention is to provide a pigment ink capable of obtaining excellent image quality.
• the ink jet recording method has the same width as the “recording head length” by reciprocally scanning the recording head in the main scanning direction more than once in order to improve the image quality.
• the method of recording the image hereinafter referred to as multi-pass recording) 'is performed.
• the printing time may not be sufficiently shortened even if the number of nozzles is increased or the printing head length is increased. Therefore, in order to shorten the recording time, a method of recording in both the forward and backward directions of the main scan (hereinafter referred to as reciprocal recording) and the length of the recording head in one main scan are the same. Attempts have been made to record wide images (hereinafter referred to as 1-pass recording). Recording is performed by combining 1-pass recording and reciprocal recording, that is, 1 inch. By performing reciprocal recording, it is not necessary to scan the same portion on the recording medium a plurality of times, so that the recording time can be greatly shortened.
• the third object of the present invention is to suppress the occurrence of back-and-forth unevenness when forming an image by reciprocal recording, in addition to solving the first and second problems. It is to provide a pigment ink that can be used.
• Another object of the present invention is to provide an ink set, an ink jet recording method, an ink cartridge, a recording unit, an ink jet recording apparatus, and an image forming method using the pigment ink.
• the discharge port of the pigment sink and the discharge port of at least one kind of reactive ink that destabilizes the dispersion state of the pigment in the pigment link are the same.
• the Y and the above in the pigment and reaction inks that cap the discharge port with the same cap satisfy the relationship of the following formula (A).
• the pigment ink according to the second object of the present invention is the above-described pigment ink, wherein the reactive ink includes a plurality of reactive inks having different mixing thickening rates, and the cap includes the pigment ink.
• the ink and the reactive ink having the smallest mixed thickening rate among the plurality of reactive inks having different mixed thickening rates are cabed with the same cap.
• the pigment sink according to the third object of the present invention is at least one kind of the plurality of reactive links having different mixing thickening rates in the pigment sink having the above-described configuration.
• the reactive ink has the same hue as at least one kind of the material ink, and the remaining reactive ink force has a hue different from that of the at least one kind of pigment ink. Further, the at least one kind of pigment ink and the mixture are mixed. It is used with a plurality of reactive inks having different thickening ratios and inks having different hues. .
• An ink set according to another embodiment of the present invention is an ink set having a plurality of inks, wherein the plurality of inks are the pigment ink and the reactive ink having the above-described configuration.
• an ink jet recording method is characterized in that the ink is a pigment ink having the above-described configuration in the ink jet recording method in which recording is performed by ejecting ink by the ink jet method. .
• an ink cartridge according to another embodiment of the present invention is characterized in that, in an ink cartridge including an ink storage portion for storing ink, the ink is a pigment ink having the above-described configuration.
• the recording unit is a recording unit comprising an ink storage portion for storing ink and a recording head for discharging ink, wherein the ink is a pigment ink. And at least one kind of reactive ink that destabilizes the dispersion state of the pigment in the pigment ink, and the recording unit includes an ejection port for the pigment ink and an ejection port for the reactive ink.
• the ink jet recording apparatus includes a discharge port of a material sink and at least one type of discharge port of a reactive ink that destabilizes the dispersion state of the pigment in the pigment link.
• the facial ink and the reactive ink are mixed in an equal volume.
• the mixing thickening rate is ⁇ (%)
• the distance between the discharge port of the pigment ink and the discharge port of the reactive ink is X (mm) ( ⁇ , X> 0)
• the Y and the X satisfy the relationship of the following formula (A). .
• an image forming method includes a pigment ink and at least one kind of reactive ink that destabilizes the dispersion state of the pigment in the pigment ink, and performs recording by an ink jet recording method.
• the pigment ink having the above-described configuration is used as the pigment ink, and an image formed by the pigment ink and an image formed by at least one kind of the reactive ink are adjacent to each other. An image formed as described above is formed.
• the image forming method includes a step of ejecting facial ink, and a step of ejecting at least one reactive ink that destabilizes the dispersion state of the pigment in the pigment ink. And an image forming method comprising: capping the discharge port of the pigment ink and the discharge port of the reactive ink with the same cap, and removing the ink in the cap.
• the mixing thickening rate is Y (%)
• the distance between the discharge port of the pigment sink and the discharge port of the reactive sink is X (mm) ( ⁇ X> 0)
• the Y and X forces in pigment ink and reactive ink to be sealed satisfy the relationship of the following formula (A).
• the first invention relating to the first object of the present invention, for use in an ink jet recording apparatus in which a pigment ink ejection port and an ink ejection port that reacts with the pigment ink are scanned with the same cap. It is possible to provide pigment inks that achieve both image quality and reliability.
• the second invention relating to the second object of the present invention, in addition to solving the first problem, it is possible to provide a pigment ink capable of obtaining an excellent image quality. . .
• the third invention relating to the third object of the present invention, in addition to solving the first and second problems, when the image is formed by reciprocating recording, the reciprocation unevenness is further improved.
• a pigment ink that can reduce the occurrence of water.
• an ink set using the above-described pigment ink an ink jet recording method, an ink cartridge, a recording unit, an ink jet recording apparatus, and an image forming method. It can.
• FIGS. 1A, 1B, and 1C are schematic diagrams of the recording head portion and the suction arch I portion when the mixed thickening rate Y and the discharge port distance X satisfy the relationship of the formula (A). .
• Fig. 2 A, 2 B, and 2 C show the model of the recording head and suction section when the mixed thickening ratio Y and the distance X between the discharge ports do not satisfy the relationship of formula (A). It is a spear.
• Fig. 3 is a graph showing the area where image quality is obtained and the area where reliability is obtained (when the same cap is used) in the conventional way of thinking.
• Fig. 4 is a graph showing areas where image quality is obtained and areas where reliability is obtained (when multiple caps are used).
• Fig. 5 is a graph showing an area where image quality is obtained and an area where reliability is obtained (when the same cap is used).
• FIG. 6 is a graph showing an area in which image quality is obtained and an area in which reliability is obtained in the present invention.
• FIG. 7 is a graph showing the relationship between the mixed thickening rate and the distance between the discharge ports in the facial and reactive inks of Examples 1 to 18 and Comparative Examples 1 to 13.
• FIG. 8 is a schematic diagram showing the relationship between the recording head and the cap.
• FIG. 9 is a schematic explanatory diagram of the ink cartridge.
• FIG. 10 is a schematic explanatory diagram of an ink cartridge.
• FIG. 11 is a schematic view showing an example of an ink jet recording apparatus.
• FIG. 12 is a schematic view showing an example of a recording head cartridge.
• FIG. 13 is a diagram showing the ejection port arrays for the pigment ink and each reactive ink in Examples 19, 20, and 23. .
• FIG. 14 is a diagram showing the exit lines of pigment inks and reactive inks in Examples 21, 22, and 24.
• FIG. 15 is a diagram for explaining the distance X between the discharge ports.
• BEST MODE FOR CARRYING OUT THE INVENTION The following is a detailed description of preferred embodiments of the present invention.
• the salt when the coloring material is a salt, the salt is dissociated into ions in the ink, but it is expressed as “contains a salt” for convenience.
• the present inventors have studied for the purpose of achieving both image quality and reliability.
• the image quality and reliability can be improved by establishing a specific relationship between the reactivity between the pigment ink and the ink that reacts with the pigment ink, and the shortest distance (distance between the discharge ports) of each ink discharge port. I found out that both sexes can be achieved.
• the first invention according to the first object of the present invention has been achieved.
• the second invention according to the second object of the present invention has been achieved.
• reciprocal unevenness means that in the ink jet recording method, when recording is performed using a method in which the ink is applied differently in forward recording and backward recording, the order in which ink is applied in forward recording and backward recording is different. This is the color unevenness caused by. -.
• the pigment ink according to the present invention is used together with a reactive ink (hereinafter sometimes simply referred to as “reactive ink”) that stabilizes the dispersion state of the pigment in the material ink.
• the reactive ink preferably includes a component that destabilizes the dispersion state of the pigment.
• a component that destabilizes the dispersion state of the pigment a dye that destabilizes the dispersion state of the pigment, or a pigment Dispersed state It is possible to use a reactive component that destabilizes.
• the mixing thickening rate is Y (%) and the distance between discharge ports is X (mm) (where X> 0)
• the discharge ports are capped at the same angle of 7 °.
• Y and X satisfy the relationship of the following formula (A). The details of the mixed thickening rate Y (%) and the distance between discharge rods X (mm) will be described later.
• the above-mentioned ⁇ and the above X are further represented by the following formulas (1) and (2): ) Is satisfied.
• the mixed thickening rate ⁇ and the distance X between the discharge ports are used.
• the mixture thickening rate Y and the distance X between the discharge ports satisfy a specific relationship. The reason why both the image quality and the reliability can be improved will be shown.
• the image quality in images formed using facial and reactive inks is related to how strongly these pigment inks and reactive inks react when they react with each other.
• “react” means that the dispersion state of the pigment in the pigment ink becomes unstable when the pigment ink and the reactive ink come into contact with each other and mix. Specifically, this means that phenomena such as aggregation and precipitation of the pigment and increase in viscosity of the pigment ink occur.
• the reactivity of the pigment and reactive inks is expressed using the mixed increase viscosity described below.
• the mixing thickening rate is the rate of increase in viscosity compared to the average viscosity of the pigment ink and reactive ink when the pigment ink and reactive ink are mixed in an equal volume, and the unit is “%”.
• the mixed thickening rate is calculated from the average of the viscosity of the mixed ink and the viscosity of ink A and ink B based on the following formula.
• the viscosity of the mixed ink refers to the viscosity of the liquid (mixed ink) after mixing ink A and ink B in equal volumes and stirring for 30 minutes.
• the average viscosity of ink A and ink B is a value obtained by adding the viscosity values of ink A and ink B and dividing by the number of inks (here 2).
• the viscosity was measured using a VISCONICED type (manufactured by Tokyo Keiki Co., Ltd.) at a temperature of 25 ° C.
• the ink jet recording device has an exclusion means for removing ink in the cap, the influence of aggregates and precipitates generated by the reaction of pigment and reactive ink in the cap. Therefore, reliability may not be obtained.
• the structure necessary for removing the ink in the cap that is, the tube, the pump, and the member for holding the waste ink, aggregates and precipitates generated by the reaction of the pigment ink and the reactive ink. The role may be lost due to the influence of goods, and reliability may not be obtained.
• the mixed thickening rate Y (%) is a value for a plurality of inks that react with each other, and therefore is assumed to be greater than 0.
• the lower limit of the mixed thickening ratio Y is 10% or more, more preferably 13% or more, and particularly 18% or more. It is preferable that When the lower limit of the mixed thickening ratio Y is lower than 10%, the reactivity of the pigment ink and the reactive ink is low, and the effect of improving the image quality such as the anti-blending property may not be obtained.
• the upper limit of the mixing thickening rate Y is preferably 70% or less, more preferably 66% or less, and particularly preferably 60% or less. If the upper limit of the mixing thickening ratio Y is higher than 70%, sufficient reliability may not be obtained.
• the distance between discharge ports is the distance between the discharge port of the pigment ink and the discharge port of the reactive ink.
• the distance between the ejection openings when ink A and ink B are two types of ink that react with each other is as follows.
• the distance X between the discharge ports in the present invention will be described with reference to FIG. That is, the distance between discharge ports 3 8 is the distance indicated by the arrow in FIG. 15, that is, the discharge port for ink A in the discharge port 3 7 for discharging ink A and the discharge port 3 9 for discharging ink B.
• the unit is “mmj.” If there are multiple discharge ports that discharge ink A and ink B, the “ The distance between the discharge ports where the distance between the edge of the discharge port of ink A and the edge of the discharge port of ink B is the shortest. Since the discharge port distance X (mm) is a value indicating the distance, it is assumed to be larger than 0 (that is, X> 0). In the present invention, the lower limit of the distance X between the discharge ports is preferably larger than 0.8 mm, and more preferably 1.5 mm or more, and the upper limit of the distance X between the discharge ports is 26. O mm or less, more preferably 22.2 mm or less.
• the upper limit of the distance X between the discharge ports is preferably 26.Omm or less. Also, if the distance between the ejection ports is too large, the time interval for applying the pigment ink and the reactive ink to the recording medium becomes large, so that when these inks contact each other, As a result, the effects of the present invention may not be sufficiently obtained.
• the mixed thickening rate Y and the discharge port distance X satisfy the relationship of the following formula (A). (However, X> 0).
• Formula (A) shows that when the distance X between the discharge ports is large, the mixing thickening rate Y is large, that is, even when the combination of the pigment ink and the individual reaction ink is high, excellent reliability is obtained. It is shown that.
• the influence of the relationship between the mixing thickening rate Y and the discharge port distance X on the reliability will be described with reference to FIGS. 1A, 1B, 1C, 2A, 2B, and 2C. .
• FIG. 6 is a schematic diagram of a suction portion that is a recording head portion and a removal portion for removing ink from the cap when the inter-mouth distance X satisfies the relationship of the formula ( ⁇ ).
• Figure 1 1 shows the ink flow when ink is sucked through the cap. In the recording head 100 0 0, as shown by the arrow in FIG.
• FIG. 1A shows a state in which the reactive component 100 6 in the reactive ink and the pigment 100 7 in the pigment ink are sucked immediately after the ink suction is started through the cap.
• FIG. 1C shows a state in which suction is further performed in addition to the state force of FIG. 1B.
• reactant walls 1 0 0 8 are formed. Then, after the reactant wall 10 8 is formed, the pigment in the pigment ink and the reactive component in the reactive ink do not contact each other due to the presence of the reactant wall. The state of 1 C will be maintained. In the present invention, it is considered that excellent reliability can be obtained by the mechanism described above. '
• the reliability may be lowered. This is thought to be because the following phenomenon occurs when reactive ink and pigment ink errors occur due to the suction operation. That is, because the pigment and reactive components form a reactant in the space formed by the recording head and cap, the reactant is captured by the reactant wall before aspiration is performed. The reactant wall grows and a mass of reactant is formed. In addition, the reaction mass may grow and adhere to the recording head, reducing reliability. Therefore, excellent reliability can be obtained when the mixing thickening ratio Y and the distance X between the discharge ports satisfy the relationship defined by the present invention.
• FIG. 6 is a schematic diagram of a recording head portion when the distance between the mouths does not satisfy the relationship of formula (A), and a suction portion that is an exclusion means for removing ink from the cap.
• Figure 2A shows the ink flow when ink is sucked through the cap.
• the reactive ink is discharged from the discharge port 1 0 0 1 force
• the pigment ink is discharged from the discharge port 1 0 0 2 as shown by the arrow in FIG. It is sucked through 0 0 3 and the absorbent body in the cap 1 0 0 5 and further through the tube 1 0 0 4.
• FIG. 2B shows a state in which the reactive component 100 6 in the reactive ink and the pigment 1 0 0 7 in the pigment ink are sucked immediately after the ink suction is started through the cap. .
• the reactive ink and the pigment ink come into contact with each other and mix.
• FIG. 2C shows a state in which suction is further performed from the state of FIG. 2B.
• the effect of obtaining excellent image quality in the present invention can be obtained more prominently when an image is formed by applying a reactive ink to a recording material prior to a pigment ink. However, even when the ink is applied to the recording medium prior to the reactive ink to form an image, the effect of obtaining the excellent image quality of the present invention is still obtained.
• the effect of improving is low. Since the interval at which the reactive ink and the pigment ink are applied to the recording medium depends on the distance between the ejection ports, the greater the distance between the ejection ports, the higher the reactivity of the reactive ink and the pigment ink. It is necessary to increase the thickening rate. As described above, the interval at which the reactive ink and the pigment ink are applied to the recording medium is closely related to the image quality. The interval at which the ink is applied to the recording medium is related to the distance between the discharge ports and the mixing thickening rate.
• the distance between the discharge ports and the mixing thickening rate affect the image quality in addition to the reliability.
• the cap also serves as an ink suction mechanism as an exclusion means for removing ink, it is not possible to cap each ejection port that ejects a plurality of inks that react with each other with the same cap. It was considered impossible.
• FIG. 3 is a conceptual diagram showing an area where image quality can be obtained and an area where reliability can be obtained (when the same cap is used) in the conventional concept as described above.
• the vertical axis is the mixed thickening rate Y (%)
• the horizontal axis is the distance between discharge ports X (mm).
• the distance between discharge ports on the horizontal axis represents a general range of the distance between discharge ports considered to be preferable to use the same cap as described above.
• FIG. 4 is a graph showing an area where image quality can be obtained and an area where reliability can be obtained (when a plurality of caps are used).
• the vertical axis is the mixed thickening rate Y (%)
• the horizontal axis is the discharge port distance X (mm).
• the discharge port distance X which is the horizontal axis, uses a plurality of caps, it is shifted to a range larger than the range of the discharge port distance that is considered to be preferable to use the same cap.
• FIG. 5 is a graph showing an area where image quality can be obtained and an area where reliability can be obtained (when the same cap is used).
• the vertical axis is the mixed thickening rate Y (%)
• the horizontal axis is the distance between discharge ports X (mm).
• the discharge port distance X which is the horizontal axis, represents a general range of the discharge port distance range in which it is considered preferable to use the same cap, as in FIG. In Fig.
• FIG. 6 is a graph showing an area where image quality is obtained and an area where reliability is obtained according to the present invention. '
• Line 7 in Fig. 6 shows the minimum distance between discharge ports that can be realized with the current technical level.
• the minimum value of the distance between the outlets is limited from the viewpoint of the process of forming the outlet array and the reliability of the recording head. There is.
• the distance between the discharge port and the end of the plate requires a certain amount of distance, and since a “gap” is required to attach multiple plates together, the distance between the discharge ports is still the minimum. There is a limit to the value.
• the minimum distance between the discharge ports that can be realized with the current technical level in the present invention is determined. If the technical level improves and the minimum distance between the discharge ports can be reduced, the minimum value of the distance between the discharge ports is smaller than the range of the following formula (1) unless the effect of the present invention is impaired. You can make it smaller. However, Since the distance between discharge ports X (mm) is a value indicating the distance, it should be greater than 0.
• a straight line 8 in FIG. 6 shows the relationship between the discharge port distance and the mixing thickening rate in order to obtain image quality.
• the mixing thickening rate is larger than this boundary line, the plurality of inks that react with each other have sufficient reactivity, and excellent image quality can be obtained.
• the mixing thickening rate is smaller than this boundary line, the reactivity of the plurality of inks that react with each other is insufficient, and the effect of using the reactive ink cannot be obtained.
• the reason for this is as follows.
• the ink previously applied to the recording medium penetrates in the depth direction of the recording medium as time passes. If the distance between the ejection ports is large, that is, if the time difference in which a plurality of inks that react with each other is applied to the recording medium is large, the plurality of inks that react with each other are mixed slowly. As a result, in the depth direction of the recording medium, a reaction occurs at the sinked portion, and an excellent image quality may not be obtained. For this reason, it is necessary to increase the reactivity of a plurality of inks that react with each other so that the reaction occurs as soon as possible after the ink is applied to the recording medium.
• the reactive ink when the reactive ink is applied to the recording medium before the pigment ink, a phenomenon different from the above phenomenon occurs.
• the reactive ink is applied to the recording medium first, the reactive ink is applied to increase the ink permeability of the recording medium, and then the pigment ink is applied to the recording medium. .
• the pigment ink since the pigment ink is more likely to penetrate into the depth direction of the recording medium, it is necessary to increase the reactivity in order to improve the image quality.
• the ink permeability of the recording medium is enhanced by the reactive ink being applied to the recording medium. ing.
• the pigment ink penetrates on the recording medium so as to be drawn into a region where the permeability is enhanced by the application of the reactive ink.
• a phenomenon occurs in which the boundary between the image formed with the pigment ink and the image formed with the reactive ink is blurred in white. Therefore, when the reactive ink is applied to the recording medium before the pigment ink, it is necessary to increase the reactivity as the distance between the ejection ports is increased.
• the straight line 9 in Fig. 6 shows the relationship between the discharge port distance and the mixing thickening rate in order to obtain reliability.
• the mixing thickening rate is larger than this boundary line, they react with each other Reliability is not obtained because the reactivity of multiple inks is too high. Further, when the mixing thickening rate is smaller than this boundary line, the reactivity of a plurality of inks that react with each other is appropriate, and excellent reliability can be obtained.
• the discharge port of the pigment ink and the discharge port of the reactive ink were respectively cabbed with different caps, so that the sticking by the mist had a great influence on the reliability.
• the distance between the discharge ports becomes larger, sticking due to mist during recording is less likely to occur, so that the waviness thickening rate can be increased.
• the relationship between the distance between the discharge ports and the mixing thickening rate in order to obtain the conventional image reliability was a boundary line indicated by the straight line 4 in FIG.
• a boundary line for obtaining reliability was obtained. That is, even when the distance between the discharge ports of a plurality of inks that react with each other is large and the mixing thickening rate is large, a boundary line that can obtain reliability is obtained.
• the boundary line of this reliability is the distance between the ejection ports when wiping multiple ejection ports that react with each other with the same wiper when no special mechanism is used in the wiping mechanism using the wiper. It is also the relationship between the mixing thickening rate.
• the above three conditions are expressed by the following formula (1):
• the reactivity between the pigment ink and the ink that reacts with the pigment ink, that is, the mixing thickening rate, and the distance between the ejection openings of the respective inks have a specific relationship.
• the combination of the conventional pigment ink and the ink that reacts with the pigment ink has high reactivity with respect to the distance between the ejection ports, that is, the mixing thickening rate is large, and therefore does not satisfy the provisions of the present invention. .
• the composition of the pigment ink and the reactive ink is selected so that the dispersion state of the pigment in the pigment ink becomes unstable when the pigment ink and the reactive ink are mixed.
• the reactive ink contains a dye that destabilizes the dispersion state of the pigment in the Tateshina ink
• the reactive ink contains a reactive component that destabilizes the dispersion state of the pigment in the pigment ink, and the like.
• the above-described aspect (1) can be, for example, the following (A), (B), or (C), and the aspect (2) described above is specifically Can be, for example, (D) or (E) below.
• the cationic group of the dye reacts with the anionic group of the pigment, causing dispersal destruction and agglomeration of the additive and increasing the viscosity of the ink.
• (C) An embodiment in which the pigment in the pigment ink has an anionic group, and the dye in the reactive ink has an anionic group having many solubilizing groups.
• the counter ion (cation) of the dye reacts with the anionic group of the pigment to cause dispersion destruction and aggregation of the pigment, and the ink is thickened.
• the pigment in the pigment ink has an anionic group
• the reactive ink contains, for example, a polyvalent metal as a reactive component.
• the cation (polyvalent metal ion) constituting the polyvalent metal salt reacts with the anionic group of the pigment to cause dispersion destruction and aggregation of the pigment.
• the ink thickens.
• the polyvalent metal salt exists in the ink by dissociating into a polyvalent metal ion and anion, but in this case, it is expressed that the ink contains the polyvalent metal salt.
• a specific means for the ink to contain a polyvalent metal is, for example, that the ink contains a polyvalent metal salt.
• the polyvalent metal Ion specifically, for example, Mg 2 +, Ca 2+, Cu 2+, Co 2 +, N i 2 +, F e 2 +, L a 3+, Nd 3 +, Y 3+ and A 1 3 + .
• the anion specifically, for example, N0 3 primary, S0 4 2 one is preferably a C 1-.
• the polyvalent metal ions described above are used.
• Mg 2+ is particularly preferred.
• N0 3 1, S. 0 4 2 —, C 1— since the solubility in water is excellent, It is particularly preferable to use NO 3.
• the content (mass%) of the polyvalent metal in the reactive ink is preferably from 0.01 mass% to 10.0 mass% based on the total mass of the reactive ink. In the form of salt, the content is preferably 0.1% by mass or more and 15.0% by mass or less.
• (E) pigment in the pigment ink is stable dispersed at p H A
• a reactive ink is p H B
• mixed Inku obtained by mixing the reactive Inku the pigment Inku is p H c A mode in which the pH of each ink is adjusted.
• pH A is a pH region where the pigment dispersion is stable
• pH C is a pH region where the pigment dispersion is unstable.
• the pigment ink according to the present invention By using the pigment ink according to the present invention together with one kind of reactive ink, sufficiently excellent image quality and reliability can be obtained.
• the reactivity of the pigment ink and the reactive ink that is, the mixing thickening rate is suppressed within a certain range, so that the pigment ink ejection port and the reactive ink ejection port are reduced.
• the same cap For this reason, there is a limit to the improvement of image quality when only one type of reaction mixture is used. Therefore, in order to obtain further excellent image quality, it is particularly preferable to use at least two types of reactive inks that stabilize the dispersion state of the pigment in the pigment ink.
• a reactive ink having a relatively large mixing thickening ratio is a strong reactive ink, and a mixed thickening ratio is relatively high.
• a small reactive sink is defined as a weak reactive sink.
• the discharge port of the weak reactive ink with the lowest reactivity should be the same as the discharge port of the pigment sink. Caving is preferred.
• the discharge port of the strongly reactive ink can be capped with the same cap as the discharge port of the pigment ink or a different cap.
• the distance between the discharge port of the pigment ink and the strongly reactive ink is X (mm)
• the mixing thickening ratio of the pigment ink and the strongly reactive ink is Y (%). It is preferable to satisfy the relations 1) and (2).
• the distance between the ejection ports is relative to the reactivity.
• the distance between the discharge ports of the strongly reactive ink and the pigment ink having a relatively high mixing thickening rate must be larger than the distance between the discharge ports of the weakly reactive ink and the pigment ink. . This is because, as described above with respect to the boundary line of the image quality, the image quality when using a plurality of inks that react with each other is related to the reactivity, that is, the mixing thickening rate and the distance between the ejection ports. .
• the distance between the ejection ports is longer when using strong reactive ink than when using weak reactive ink. It needs to be bigger. In this way, by setting the distance between the ejection openings according to the reactivity of the ink, it is possible to form a similar image even when an ink having a different reactivity is used as the reactive ink used in combination with the pigment ink. it can. This also improves the reliability.
• the discharge port of the pigment ink is set at a position between the discharge ports of the two types of reactive inks. This is because, when performing reciprocal recording, it is possible to reduce reciprocal unevenness by always making the order in which the pigment ink and the reactive ink are applied to the recording medium.
• the reactive ink preferably has the same hue as the pigment ink.
• at least one type of reactive ink has the same hue as the pigment ink.
• the reactive ink is S with the same cap as the discharge port of the pigment sink, and that the hue is the same as that of the pigment sink. This is because, when the same cap is used for caving with the same cap, if the pigment ink and reactive ink have the same hue, even if the pigment ink and reactive ink are mixed, the color developability of the image at the beginning of recording, etc. This is because problems are unlikely to occur.
• the ink of the present invention a pigment ink and a reactive ink are superimposed on a recording medium, and these inks react with each other to obtain excellent image quality and bleeding resistance. Therefore, the ink of the present invention
• the image formed using is a mixture of pigment and reactive ink color materials. At this time, when the pigment ink and the reactive ink do not have the same hue, it is not preferable because a color material having a different hue is applied to the recording medium in an overlapping manner, resulting in an image different from the hue of the pigment ink.
• the reactive ink has a hue different from that of the pigment ink
• the pigment ink has a black hue and the reactive ink has a cyan hue, for example, a magenta ink or a yellow ink is superimposed on the area where the reactive ink is applied on the recording medium. It is preferable to adjust.
• the fact that the pigment ink and the reactive ink have the same hue means the following.
• the pigment ink is a black ink
• the chroma difference AC * between the pigment ink and the reactive ink is 0 or more and 15 or less, preferably 0 or more and 10 or less. If the saturation difference is larger than this, the hue of the reactive ink becomes clear, so when mixing with the pigment ink, the hue of the image to be formed differs due to the influence of the hue of the reactive ink. May be.
• the pigment ink is a force ink
• the difference in hue angle between the pigment ink and the reactive ink A h force is 0 or more and 60 or less, preferably 0 or more and 30 or less.
• the difference in hue angle is larger than this, the difference in hue between the pigment ink and the reactive ink becomes large, and when mixed with the pigment ink, the hue of the image to be formed is affected by the influence of the hue of the reactive ink. May be different.
• the lightness L * of the ink is preferably a value close to that of the pigment ink.
• a combination of inks in which the pigment ink and the reactive ink have the same hue for example, a case where both the pigment ink and the reactive ink are black inks can be cited. That the reactive ink has a different hue is out of the above range.
• the reactive ink is a magenta ink or a yellow ink. Recognize that it is cyanink.
• the pigment ink and the reactive ink are both black inks.
• the pigment ink and the reactive ink are both black inks.
• at least one type of reactive ink and pigment ink are both black inks.
• the black ink, which is a reactive ink is a weak reactive ink
• the cyan ink is a strong reactive ink.
• the pigment ink is black ink, and the reactive ink that is capped with the same cap as the discharge port of the pigment sink is black ink. .
• the discharge volume of the pigment ink and the reactive ink it is preferable to reduce the discharge volume of the pigment ink and the reactive ink.
• the reason is as follows.
• the discharge volume of the pigment ink is small, the surface area of the ink droplet is increased, and the aqueous medium constituting the ink is quickly evaporated before adhering to the recording medium.
• the dispersion state of the pigment becomes unstable along with the evaporation, so that the dispersion state of the pigment ink alone becomes more unstable as the discharge volume becomes smaller. If the reaction is in contact with the reactive ink in an unstable dispersion state, the instability of the dispersion state is further accelerated, and the image quality is improved. To get this effect, face It is preferable that the ink discharge volume be 5 p 1 or less.
• the discharge volume of reactive ink is preferably 5 p 1 or less.
• the viscosity of the pigment ink and the reactive ink is set to 5 m Pa in order to obtain ejection stability and to make the viscosity of the mixed ink appropriate. It is preferable to set it as s or less.
• the color material used for the pigment ink is preferably one bon black for the black ink and the organic pigment is preferably used for the pigment other than the black ink.
• the pigment dispersion in the pigment ink may be any of a self-dispersion type, a resin dispersion type using a resin or the like as a dispersant, and the like. These pigments may be used alone or in combination of two or more. In addition to pigments, dyes can be used for purposes such as toning.
• the content (% by mass) of the pigment in the pigment ink is 0.1% by mass or more and 15.0% by mass or less, and further 1.0% by mass or more and 10.0% by mass, based on the total mass of the pigment ink. % Or less is preferable.
• a self-dispersing pigment in which at least one hydrophilic group is bonded to the surface of the pigment particle directly or through another atomic group (one R—).
• R— another atomic group
• the hydrophilic group bonded to the surface of the pigment particle is, for example, —CO 2 O (M X ) -S0 3 (M, -PO3H (MJ, 1 P0 3 (Mj 2 , 1 (C OO (MJ) n, etc.
• MJ is a hydrogen atom, an alkali metal, an ammonia, or an organic ammonium
• n is an integer of 2 or more.
• — Includes an alkylene group having 1 to 12 carbon atoms, a substituted or unsubstituted phenylene group, or a substituted or unsubstituted naphthylene group
• the present invention is not limited thereto.
• the present invention is not limited to this, and the form of the hydrophilic group in the ink may be in any of a partly dissociated state or a completely dissociated state. ..
• a material obtained by the diazo coupling method and having the above-described compound having a structure of one R— (COOM,) n group in part as a surface can be suitably used.
• the present invention is not limited to this. '
• a self-dispersing pigment in which one R— (COOM n group is bonded to the surface of the pigment particle, since excellent image quality and pre-fixing resistance can be obtained.
• the interaction between the self-dispersing pigment and the water-soluble organic solvent in the ink is greatly involved, ie, one R— (COOM n group is bonded to the surface of the pigment particle.
• the one R— (COOMJ n group is bonded at a higher density to the surface of the pigment particle, the following phenomenon is considered to occur.
• the ink comprising sterically hindered like easily occurs in the presence of one R- (COOM n group bonded to the surface of the pigment particle. Therefore, one R- (C OOM n is bound to the pigment particles and their The water-soluble organic solvent present in the vicinity is more soluble than conventional self-dispersing pigments and water-soluble organic solvents present in the vicinity. It becomes difficult to meditate. As a result, it is considered that when the ink is applied to the recording medium, separation (solid-liquid separation) between the aqueous medium in the ink and the solid content including the pigment is caused very rapidly.
• the solvation in the present invention means the affinity between the pigment and the water-soluble organic solvent. It depends on how much the pigment has an affinity for the water-soluble organic solvent.
• the site having affinity for the water-soluble organic solvent include a site where a hydrophilic group is not bonded on the surface of the pigment particle. For example, when ionic groups are bonded to the surface of the pigment particles at a high density, the area where the portion having affinity for the water-soluble organic solvent is exposed on the surface of the pigment particles is small.
• the hydrophilic group covers the surface of the pigment particle at a higher density, the following occurs.
• the water-soluble organic solvent is difficult to solvate with respect to the pigment due to the synergistic effect of the effect of steric hindrance due to the hydrophilic group and the effect of the reduction of the portion of the pigment having affinity for the water-soluble organic solvent.
• one carbon atom adjacent to the carbon atom to which CO OMJ is bonded is preferably one (CO OM bonded.
• the n is preferably 2, and the R is preferably C 6 H 3.
• the above-described configuration can provide excellent effects on image quality and bleeding resistance.
• one (the carbon atom adjacent to the carbon atom to which the CO OM is bonded is Two or more adjacent carbon atoms in R each have one (CO OM group. Specifically, this has a structure represented by the following formula (1). In the group represented by the following formula (1) on the surface of the pigment particles: It is preferable to use a self-dispersing pigment in which is bonded. Of course, the present invention is not limited to this.
• the one R— (COOM n group is bonded to the surface of the pigment particle at a higher density.
• the hydrophilic group on the surface of the pigment particle is used.
• the density is preferably 2.0 ⁇ mo 1 Zm 2 or more, which is because the solid-liquid separation due to the degree of solvation described above is further promoted, and the above-described effects can be obtained more remarkably.
• the hydrophilic group density in the pigment particles is greatly influenced by the specific surface area of the pigment, the structure of the functional groups bonded to the surface of the pigment particles, and the like. It is not limited to the range.
• the self-dispersing pigment in which is ammonium can be obtained by the following method. For example, for self-dispersing pigments where I ⁇ is an alkali metal, JN ⁇ is replaced by ammonium by the ion exchange method, or ammonium hydroxide is added after adding acid to form H. For example, hesitates to make ammonium.
• the following can be used as the dispersant.
• Styrene-acrylic acid co-child combination styrene-acrylic acid-acrylic acid alkynole esterol copolymer.
• Styrene monomaleic acid copolymer styrene monomaleic acid-acrylic acid alkyl ester copolymer.
• Styrene-methacrylic acid copolymer styrene-methacrylic acid monoacrylic acid alkyl ester copolymer.
• Styrene monomaleic acid half ester copolymer Burnaphthalene-acrylolic acid copolymer, vinyl naphthalene monomaleic acid copolymer, styrene monomaleic anhydride-maleic acid half ester copolymer. Or salts of these copolymers.
• the pigment used for the black ink examples include carbon black.
• furnace black, lamp black, acetylene black, or channel black can be used as the carbon black.
• the following commercial products can be used.
• the present invention is not limited to these.
• Carbon black newly prepared for the present invention can also be used. Further, the present invention is not limited to carbon books, and magnetic fine particles such as magnetite and ferrite, titanium black, and the like may be used.
• Examples of the pigment used in addition to the black ink include various organic pigments. Specifically, for example, the following can be used as the organic pigment.
• Water-insoluble azo pigments such as Torayzin 'Red, Tonoleidin Manolene, Nonza Yellow, Benzine Yellow, and Phizolone Red.
• Water-soluble azo pigments such as small red, helio bordeaux, pigment scarlet, and permanent red 2B. Derivatives from vat dyes such as alizarin, indanthrone and thioindigo maroon.
• Phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green.
• Quinacridone pigments such as quinacridone red and quinacridone magenta.
• Perylene-based materials such as perylene red and perylene scarlet.
• Isoindolinone pigments such as Soindolinone Yellow and Isoindolinone Orange.
• Imidazo mouth pigments such as benzimidazolone yellow, benzimidazolone orange, and benzimidazolone red.
• Pylanthrone pigments such as Pyranthron Red and Pyranthrone Orange.
• Indigo pigment Condensed azo-based materials. Thioindigo pigment. Diketopyrrolopyrrole pigment. Flavanthrone Yellow, Asinoleami Doellow, Kinofuta Mine Yellow, Nickel Azoyer
• Rho copper azomethine yellow, perinone orange, anthrone orange, dianthraquinonyl red, dioxazine violet, etc.
• organic pigments that can be used in the present invention are indicated by the color index (CO LOUR I NDEX) number, and the following can be mentioned.
• the pigment ink preferably contains a salt.
• a pigment ink that does not greatly change the image quality depending on the type of the recording medium, has a high image density, and can stably obtain an excellent image quality.
• the image densities are almost equal, It is possible to form an image that is not visually uncomfortable.
• the form of the salt in the pigment ink may be any form in which a part thereof is dissociated or completely dissociated.
• salts that can be used in the pigment ink include, for example, (M 2 ) N 0 3 , CH 3 COO (M 2 ), C 6 H 5 C 0 0 (M 2 ), C 2 H 4 (COO (M 2 ) ) 2 , C 6H 4 (COO (M 2 )) 2 , (M 2 ) 2 S0 4, etc.
• M 2 is an alkali metal, an ammonium, or an organic ammonium.
• the present invention is not limited to these.
• the content of the salt in the pigment ink may be within a range where the effects of the present invention can be sufficiently obtained.
• the salt content (mass%) is 0.05 mass% or more and 10.0 mass based on the total mass of the ink. / Preferably less than 0 . If the content is less than 0.05% by mass, the effect of the present invention may not be obtained. If the content is more than 10.0% by mass, the storage stability of the ink may not be obtained.
• M 2 is ammonium
• NH 4 N0 3, C 2 H 4 ( CO_ ⁇ _NH 4) 2,. C 6 H ⁇ (COONH 4) 2, (NH 4) 2 S_ ⁇ 4 such a relatively short time, water resistance expression Therefore, it is particularly preferable.
• the salt is C 2 H 4 (COO (M 2 )) 2 , C 6 H 4 (COO (M 2 )) 2 , (M 2 ) 2 S 4
• the dispersion stability of the pigment is particularly excellent, which is more preferable.
• a divalent salt is used as a salt used in combination with the self-dispersing pigment.
• a divalent salt is used as a salt used in combination with the self-dispersing pigment.
• the valence of the functional group on the surface of the pigment particle and the valence of the salt are the same, since the effects of the present invention can be obtained more remarkably.
• One R— (COOM 2 group bonded to the pigment particle surface, C 2 H 4 (C OO (M 2 )) 2 , C 6 H 4 (COO (M 2 )) 2 , (M 2 ) 2 S0 4 and les, a combination of salt A combination etc. are mentioned.
• the present invention is not limited to this.
• the pigment ink is preferably water or an aqueous medium that is a mixed solvent of water and a water-soluble organic solvent. It is preferable to use deionized water instead of general water containing various ions.
• the water content (mass%) in the pigment ink is 5 mass% to 95 mass% based on the total mass of the pigment ink. / 0 or less is preferable.
• the water-soluble organic solvent is particularly preferably one having an effect of preventing ink drying.
• the content (% by mass) of the water-soluble organic solvent in the pigment ink is preferably 3.0% by mass or more and 50.0% by mass or less based on the total mass of the pigment ink.
• the following water-soluble organic solvents can be used.
• the following water-soluble organic solvents can be used alone or as a mixture.
• Alkylene groups such as ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1, 2, 6 hexane triol, diglycol, hexylene glycol, diethylene glycol, etc. have 2 to 6 carbon atoms
• Alkylene diol acetates such as polyethylene glycol monomethylenole ether acetate, etc.
• the pigment ink may use a moisturizing compound such as urea, urea derivative, trimethylolpropane, and trimethylolethane in order to maintain the moisturizing property.
• a moisturizing compound such as urea, urea derivative, trimethylolpropane, and trimethylolethane
• Urea content of the urea derivative, moisture compounds such as trimethylolpropane (wt. / 0) are generally, based on the pigment ink total mass, 0. 1 mass% or more 2 0. 0 wt% or less, further Is preferably 3.0% by mass or more and 10.0% by mass or less.
• the pigment ink may contain various compounds as necessary in addition to the above-described components in order to obtain an ink having a desired physical property value.
• Specific examples include surfactants, pH adjusting agents, antifoaming agents, antifungal agents, antiseptics, antifungal agents, antioxidants, reduction inhibitors, evaporation accelerators, chelating agents, and the like. It is done. Further, a water-soluble dye or the like can be added to the pigment ink.
• the scratch resistance of the image and the marker resistance can be improved.
• a nonionic polymer having no ionic group has little influence on the reliability of the ink and can be suitably used. .
• the reactive ink used in the present invention needs to have an action of destabilizing the dispersion state of the pigment in the pigment ink.
• the reactive ink contains a dye that destabilizes the dispersion state of the pigment in the pigment ink, and (2) the reactive ink force, the dispersion state of the pigment in the pigment ink is improper. It is preferable to adopt either one of the constitutions containing a reactive component or the like to be stabilized. More specifically, the reactive ink has any one of the constitutions (A) to (E) described above. It is preferable that
• the color material used for the reactive ink is preferably a dye, specifically, an acid dye, a direct dye, or the like. Dyes can be used as long as they have an appropriate color tone and concentration, whether existing or newly synthesized, and can be used alone or as a mixture.
• the content (mass./o) of the coloring material in the reactive ink of the present invention is based on the total mass of the reactive ink.
• 0.1 mass. / 0 to 10.0% by mass is preferred.
• the content is less than 0.1% by mass, sufficient image quality may not be obtained, and when the content exceeds 10.0% by mass, fixing recovery may not be obtained.
• each M is independently a hydrogen atom, an alkali metal, an alkaline earth metal, a cation of an organic amine, or an ammonium ion, and each n is independently 1 or 2.
• each M is independently a hydrogen atom, an alkali metal, an alkaline earth metal, a cation of an organic amine, or an ammonium ion.
• the alkali metal include, for example, sodium, force lithium, lithium and the like.
• Specific examples of the alkaline earth metal include calcium and magnesium.
• the organic amine include, for example, methylamine, ethenoreamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, disopropanolamine and the like.
• M is a hydrogen atom, an alkali metal such as sodium, force lithium, lithium, etc., an ammonium ion, monoethanolamine, jetanolamine, triethanolamine, etc. It is preferably a force noramine ion or the like.
• R 2 , R 3 , R 4 , R 5 and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a carboxyl group (provided that R 2 , R 3 , R 4 , R 5 , and R 6 are all hydrogen atoms. Except in some cases.)
• the following exemplary compounds M1 to M7 are preferred exemplary compounds of the compound represented by the general formula (III) or a salt thereof. Of course, the present invention is not limited to these. In the following exemplified compounds M1 to M7, all the solubilizing groups are described as H type, but may form a salt. Preferred specific examples of the compound represented by the general formula (III) or a salt thereof include the following exemplified compound Ml (a sodium salt) which is a sodium salt of the exemplified compound Ml. Of course, the present invention is not limited to this.
• M is an alkali metal or ammonium
• R 2 is independently a hydrogen atom, a sulfonic acid group, or a carboxyl group (provided that 1 ⁇ and R 2 are simultaneously hydrogen atoms)
• Y is a chlorine atom, a hydroxyl group, an amino group, or a mono- or dialkylamino group
• m l to 3
• n l to 3 ( However, 1 + m + n 3 to 4)
• the substitution position of the substituent is the 4-position or the 4'-position.
• M is an alkali metal or ammonium. Specific examples of the alkali metal include sodium, potassium, lithium and the like. .
• the above colorant has an unsubstituted sulfamoyl group (one S 0 2 NH 2 ) or a substituted sulfamoyl group (a group represented by the general formula (V)) only at the 4-position and the 4′-position in the general formula (IV). It is a phthalocyanine derivative introduced selectively.
• the compound represented by the general formula (IV) can be synthesized by reacting 4-sulfophthalic acid derivative, or 4-sulfophthalic acid derivative and (anhydrous) phthalic acid derivative in the presence of a metal compound.
• a phthalocyanine compound is used as a raw material. Furthermore, after converting a sulfonic acid group in the phthalocyanine compound to a chlorosulfonic acid group, it is obtained by reacting an aminating agent in the presence of an organic amine.
• substituted sulfamoyl group represented by the general formula (V) Preferred specific examples of the substituted sulfamoyl group represented by the general formula (V) are shown below. Of course, the present invention is not limited to these.
• the substituted sulfamoyl group represented by the general formula (IV) is shown in the form of a free acid.
• Preferable specific examples of the compound represented by the general formula (V) include a compound in which the exemplified substituent 1 is substituted, that is, the exemplified compound C 1 shown below, from the balance between color development and environmental gas resistance. .
• the present invention is not limited to this,
• R 2 are each independently a hydrogen atom; a hydroxyl group; an amino group; a carboxyl group; a sulfonic acid group; an alkyl group having 1 to 4 carbon atoms;
• R 3 and R 4 are each independently a hydrogen atom; an alkyl group having 1 to 4 carbon atoms; an alkoxy group having 1 to 4 carbon atoms; a hydroxyl group; a hydroxyl group or a carbon number.
• An alkyl group having 1 to 4 carbon atoms which may be substituted with an alkoxy group having 1 to 4 carbons; may be substituted with a hydroxyl group, an alkoxy group having 1 to 4 carbon atoms, a sulfonic acid group or a carboxyl group A good alkoxy group having 1 to 4 carbon atoms; or an amino group substituted by an alkyl group or an acyl group, and n is 0 or 1.)
• n 0 S_ ⁇ 3 position of H is Dearuko H It is shown. _
• '4,4'-dinitrostilbene represented by the following general formula (VIII) 2, 2, a disulfonic acid and a condensed dye of a compound represented by the following general formula (IX), or a dye obtained by reduction of the condensed dye (the counter ion of the dye after condensation or after reduction is hydrogen ion, alkali metal Ion, cation of organic amine, or ammonium ion), or a salt thereof
• M is a hydrogen atom or an alkali metal atom.
• General formula (IX) (In the general formula (IX), Ri, R 2 , R 3 , R 4 , and R 5 are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a sulfonic acid group, a carboxyl group, or 1 to 4 carbon atoms.
• the compound represented by the general formula (VI) or a salt thereof is the exemplified compound Bk 1
• the general formula (VI) It is particularly preferred that the compound represented by VII) or a salt thereof is the exemplified compound B k 2.
• the condensed dyes of the general formulas (VIII) and (IX) are C.I. Direct Orange 39.
• the reactive ink is preferably water or an aqueous medium that is a mixed solvent of water and a water-soluble organic solvent.
• the configuration can be the same as that of the aqueous medium used for the pigment ink. Content of water-soluble organic solvent in reactive ink
• Mass /. Is preferably 3.0% by mass or more and 50.0% by mass or less, based on the total mass of the reactive ink.
• the content of water in the reactive ink (mass. / 0), based on the reactive ink total mass, 5 0. 0 wt% to 9 5. Is preferably 0 mass% or less.
• a moisture retention compound such as urea, urea derivative, trimethylolpropane, trimethylolethane may be used.
• the reactive ink may contain various compounds as necessary in addition to the above-described components in order to obtain an ink having a desired physical property value. This In this case, the same compounds as those used for the pigment ink can be used.
• the other ink in the present invention includes, for example, an ink that does not contain a polyvalent metal or the like, that is, an ink that does not react with the pigment ink (non-reactive ink).
• the non-reactive ink preferably contains at least a coloring material, an aqueous medium, and the like, and the content thereof can be the same as the reactive ink described above.
• a dye as a coloring material for other inks.
• the pigment ink according to the present invention is used in an ink jet recording apparatus in which the ejection port for the pigment ink and the ejection port for the reactive ink that destabilizes the dispersion state of the pigment in the pigment ink are capped with the same cap. is required.
• the ink jet recording apparatus has a means for removing ink in order to exclude ink in the cap.
• the removing means for removing the ink in the cap is a removing means for removing the ink in the cap by joining a tube connected to the suction pump to the cap. Is preferred.
• the cap preferably has a member for absorbing ink in the cap.
• FIG. 8 is a schematic diagram showing the relationship between the recording head and the cap.
• the ink jet recording apparatus sucks ink by reducing the pressure inside the cap 1 1 0 7 using the suction pump 1 1 0 6 in the cap 1 1 0 7 for capping the recording head 1 1 0 1. Thereafter, the ink is sucked through the ink absorber 1 1 0 4 and the recovery tube 1 1 0 5 to become waste ink. Communication valve 1 1 0 2 and air communication hole By using 1 1 0 3 ', the reduced pressure cap 1 1 0 7 is slowly returned to the atmospheric pressure state.
• the recovery tube 1 1 0 5 can be placed anywhere in the cap 1 1 0 7. However, in order to reduce the color mixture when sucking the pigment ink and the reactive ink, it is preferable to arrange the pigment ink and the reactive ink near the center of the discharge port. Of course, the present invention is not limited to the configuration shown in FIG.
• the pigment ink according to the present invention is preferably applied to an image forming method for forming an image in which an image formed by a reactive ink and an image formed by a pigment ink are adjacent to each other.
• the pigment ink according to the present invention includes a step of discharging a pigment ink, a step of discharging at least one kind of reactive ink that destabilizes a dispersion state of the pigment in the pigment ink, and a discharge of the pigment ink. It is particularly preferable to apply the method to an image forming method that includes a step of capping the outlet and the discharge port of the reactive ink with the same cap to remove the ink in the cap.
• the pigment ink and the reactive ink that destabilizes the dispersion state of the pigment in the pigment ink are applied by the ink jet recording method so as to be mixed on the recording medium.
• the image quality can be improved.
• the occurrence of bleeding can be suppressed even in an image in which an area formed as described above and an area formed with other inks are adjacent to each other.
• the region formed with the pigment ink and the region formed with the reactive ink are adjacent, the occurrence of bleeding at the boundary between these regions can be suppressed.
• the mixing of the pigment ink and the reactive ink includes, for example, a form in which the pigment ink and the reactive ink are mixed in contact with each other in a liquid state.
• at least one of the step of applying a pigment ink to the recording medium after the reactive ink or the step of applying the reactive ink to the recording medium after the pigment ink is performed. It can be set as the form containing this process.
• the present invention is not limited to a form in which the pigment ink and the reactive ink are mixed in the body state.
• at least one of a step of applying a pigment ink to the recording medium after the reactive ink has permeated the recording medium, or a step of applying a reactive ink to the recording medium after the pigment ink has penetrated the recording medium. Can be included.
• the pigment ink and the reactive ink can be used. Is considered a mixture of
• the image forming method according to the present invention preferably includes a step of adjusting the color tone of the image as necessary.
• the ejection volume of the pigment ink and the reactive ink When forming an image, it is preferable to reduce the ejection volume of the pigment ink and the reactive ink. This is because the smaller the ejection volume, the smaller the area per dot when ink is applied to the recording medium. Therefore, when applying a certain amount of ink to a certain area of the recording medium, the degree of freedom of dot arrangement is reduced. Can be large. As a result, the pigment ink and the reactive ink can be effectively reacted. Thereby, even when an ink set having the same mixed thickening rate is used, the image quality can be further improved.
• the reactive ink or pigment ink described above is particularly preferably applied to an ink jet recording method in which ink is ejected by an ink jet method for recording.
• Ink jet recording methods include a method of ejecting ink by applying mechanical energy to ink, and a method of ejecting ink by applying thermal energy to ink.
• an ink jet recording method using thermal energy can be preferably used.
• the pigment ink according to the present invention is applied to an ink set having a plurality of inks. I prefer to do it.
• an ink set having the “pigment ink” described above and a reactive ink is preferable.
• the ink set includes not only an ink cartridge in which a plurality of ink cartridges are integrated, but also a case where a plurality of individual ink cartridges are used in combination, and further, the ink cartridge and the recording head.
• the one that is integrated is also included.
• the ink cartridge when used in combination as described below, it can be cited as an example of the ink set of the present invention.
• the above-mentioned ink-strike is used in combination with an ink cartridge containing another black ink.
• the ink cartridge is used in combination with an ink cartridge in which an ink cartridge containing black ink, light cyan ink and light magenta ink is integrated.
• ink set used in combination with a single ink cartridge and an ink cartridge containing another black ink.
• ink jet recording using the reactive ink pigment described above examples include an ink cartridge provided with an ink storage portion for storing these inks. Specific examples of ink cartridges are shown below.
• FIG. 9 is a schematic explanatory diagram of the ink cartridge.
• the ink cartridge communicates with the atmosphere through the atmosphere communication port 1 1 2 at the upper part, and communicates with the ink supply port at the lower part.
• the ink cartridge includes a negative pressure generating member storage chamber 13 4 for storing a negative pressure generating member therein, and a substantially sealed liquid storage chamber 1 36 for storing a liquid ink.
• Partition wall 1 3 8 Has a structure of partitioning.
• the negative pressure generating member storage chamber 1 3 4 and the liquid storage chamber 1 3 6 are a communication hole 1 4 0 formed in the partition wall 1 3 8 near the bottom of the ink cartridge, and a liquid storage chamber during the liquid supply operation.
• a plurality of ribs are integrally formed on the upper wall of the ink cartridge forming the negative pressure generating member accommodating chamber 1 3 4 so as to protrude inside, and compressed into the negative pressure generating member accommodating chamber 1 3 4. It is in contact with the negative pressure generating member accommodated in the state. With this rib, an air buffer chamber is formed between the upper wall and the upper surface of the negative pressure generating member.
• the ink supply cylinder provided with the liquid supply port 1 1 4 is provided with a pressure contact 1 1 4 6 having a high capillary strength and a high physical strength. Is in pressure contact.
• the first negative pressure generating member 1 3 2 B and the second negative pressure generating member 1 3 made of polyolefin resin fibers such as polyethylene are used as the negative pressure generating member.
• 2 A, 2 capillary force generating negative pressure generating members are accommodated.
• 1 3 2 C is the boundary layer between these two negative pressure generating members, and the intersection of the boundary layer 1 3 2 C with the partition wall 1 3 8 is the posture when using the ink cartridge with communication ⁇ downward
• the air introduction groove (atmosphere introduction path) is located above the upper end portion of 1 50. Further, the ink contained in the negative pressure generating member exists above the boundary layer 13 2 C as shown by the ink level.
• the boundary layer between the first negative pressure generating member 1 3 2 B and the second negative pressure generating member 1 3 2 A is in pressure, and the vicinity of the boundary layer of the negative pressure generating member The compression rate is high and the capillary force is strong. That is, the capillary force of the first negative pressure generating member 1 ⁇ 3 2 B is P 1, the second negative pressure generating member 1 3 2 A is the capillary force P 2, and the capillary having the interface between the negative pressure generating members If the power is PS, it is P 2 and P 1 and PS.
• FIG. 10 is a schematic explanatory view showing another form of the ink cartridge.
• the ink cartridge of the form shown in FIG. 10 includes, for example, a container 41 that contains three types of ink: a pigment ink, a reactive ink having the same hue as the pigment, and an ink having a hue different from the pigment, and the container 4 1. And a lid member 4 2 for covering.
• the ink cartridge has the same hue as the pigment ink, the reactive ink, the ink with a different hue from the pigment, and the ink supply port 4 3 Y, the reactive ink supply port with the same hue as the pigment. 4 3 ⁇ and an ink supply port 4 3 C with a hue different from that of the pigment.
• the inside of the container 41 is partitioned into three spaces having almost the same capacity by two partition plates 4 1 1 and 4 1 2 arranged in parallel to each other in order to accommodate three types of ink. These three spaces are aligned along the insertion direction of the ink cartridge when the ink cartridge is installed in the ink cartridge holder. In each of these spaces, an ink absorber 4 4 ⁇ that absorbs and holds the pigment ink, an ink absorber 4 4 ⁇ ⁇ that absorbs and holds the reactive ink of the same hue as the pigment, and a hue different from the pigment. Contains ink absorber 44 C that absorbs and retains ink.
• Ink supply members 45 5, 4 5, and 45 C for supplying each ink to the ink supply port are accommodated in contact with the lower part of the ink absorber.
• a recording mute suitable for performing recording using the reactive ink or pigment ink described above is a recording mute that includes an ink accommodating portion for accommodating these inks and a recording head. Can be mentioned. In particular, there is a recording unit in which the recording head causes thermal energy corresponding to the recording signal to act on the ink and generates ink droplets by the energy. '
• FIG. 11 As an ink jet recording apparatus suitable for recording using the reactive ink or pigment ink described above, an ink jet recording apparatus capable of reciprocal recording will be described with reference to FIGS. 11 and 12.
• FIG. 11 As an ink jet recording apparatus suitable for recording using the reactive ink or pigment ink described above, an ink jet recording apparatus capable of reciprocal recording will be described with reference to FIGS. 11 and 12.
• FIG. 11 As an ink jet recording apparatus suitable for recording using the reactive ink or pigment ink described above, an ink jet recording apparatus capable of reciprocal recording will be described with reference to FIGS. 11 and 12.
• FIG. 11 is a schematic explanatory view showing an example of an ink jet recording apparatus.
• the chassis 10 is composed of a plurality of plate-like metal members having a predetermined rigidity, and forms the skeleton of the ink jet recording apparatus.
• the chassis 10 includes a feeding unit 11 that feeds the recording medium, a conveyance unit 13 that guides the recording medium to a predetermined recording position and guides the recording medium to the discharge unit 12, a printing unit that performs predetermined recording on the recording medium, It incorporates a head recovery unit 14 that performs the recovery operation of the print unit.
• the print unit includes a carriage 16 that is supported so as to be able to scan along the carriage axis 15, a head cartridge that is detachably mounted on the carriage 16 via a head set lever 17, and a head cartridge that is The carriage cover 20 is positioned at the mounting position.
• One end of a contact flexible print cable (hereinafter abbreviated as contact FPC) 2 2 is connected to another engagement portion of the carriage 16 with respect to the head cartridge.
• a contact portion (not shown) formed at one end portion of the contact FPC 22 and a contact portion 301 as an external signal input terminal provided in the head cartridge are brought into contact with each other and various kinds of information are obtained. Such as supplying and receiving power and supplying power to the head cartridge.
• FIG. 12 is a schematic explanatory view showing an example of a headgage bridge.
• ink set non-reactive yellow ink, non-reactive magenta
• 1 0 1, 1 0 2, 1 0 3, 1 0 4, and 1 0 5 are respectively for strongly reactive cyan ink, non-reactive magenta ink, and non-reactive yellow ink
• discharge nozzle row for strong reactive scan ink 2 0 1 and discharge nozzle row for weak reaction black ink An example will be described with reference to 2 0.
• an electrical signal such as a recording signal is exchanged through electrical contact 3 0 1.
• 2 0 4 indicates the discharge port array of pigment black ink From the viewpoint of the number of inks used, operability, etc., it is possible to use ⁇ / do for two or more recordings in one inkjet recording device as necessary. In this case, it is possible to evaporate the ink from the nozzle. From the viewpoint of the efficiency of it and suction operation win, discharge port for Kiyabbingu the same cap are preferably arranged in head to the same recording.
• the recording head recording is performed using an electrothermal transducer (recording element) that generates thermal energy for causing film boiling to the ink in accordance with an electrical signal.
• An example of the bubble jet (registered trademark) recording head was described.
• the typical configuration and principle of the basic structure disclosed in, for example, US Pat. Nos. 4, 7 2 3 and 1 29, and 4 7 4 0 and 7 96 It is preferable to use a simple principle. This method can be applied to both a so-called on-demand type and a continuous type.
• thermal energy is generated by applying to the electrothermal transducer at least one drive signal that gives a rapid temperature rise exceeding nucleate boiling corresponding to the recorded information.
• the drive signal has a pulse shape because bubbles can be grown and contracted immediately and appropriately, and ink discharge with particularly excellent response can be achieved.
• the ink jet recording apparatus using the second mechanical energy includes a nozzle forming substrate having a plurality of nozzles, a pressure generating element made of a piezoelectric material and a conductive material disposed opposite to the nozzles, and the pressure. Ink filling the surroundings of the generating element.
• the pressure generating element is displaced by the applied voltage, and ink droplets are ejected.
• the ink jet recording apparatus can be used even if the recording head and the ink cartridge are separated, and the recording head and the ink cartridge are integrated so as not to be separated.
• the ink cartridge is integrated with the recording head so as to be separable or non-separable and is mounted on the carriage, or is provided at a fixing portion of the ink jet recording device, and is connected to an ink supply member such as a tube. You can also supply ink to the recording head.
• the ink cartridge is provided with a configuration for applying a preferable negative pressure to the recording head, the following configuration can be adopted.
• the ink jet recording apparatus may take the form of a line printer in which recording elements are aligned over a range corresponding to the entire width of the recording medium, although the serial recording method is adopted as described above.
• the resulting slurry was filtered with filter paper (Product 3 ⁇ 4: Standard filter paper No. 2; manufactured by Ryo Dobantech), and the particles were washed with water in + minutes and dried in an oven at 10 ° C for self-dispersion. Mold strength One Bon Black A was prepared. Furthermore, water was added to the self-dispersing force bomb black A obtained above to disperse the pigment concentration to 10% by mass, thereby preparing a dispersion. By the above method, a pigment dispersion A was obtained in which self-dispersing carbon black A in which one C 6 H 3 — (COONa) 2 group was introduced on the surface of the carbon black particles was dispersed in water.
• the ionic group density of the self-dispersing carbon black A prepared above was measured and found to be 3.1 ⁇ 1 / m 2 .
• the ion group density used here was measured by measuring the sodium ion concentration in Pigment Dispersion A prepared above using an ion meter (manufactured by Toa DKK), and using that value, the self-dispersing carbon black A Converted to ionic group density.
• Self-dispersing carbon black B was prepared by substituting ammonium ion for ammonium ion by the ion exchange method for pigment dispersion A obtained above. Further, water was added to the self-dispersing carbon black B obtained above and dispersed so that the facial concentration would be 10% by mass to prepare a dispersion. Above By the method, pigment dispersion B was obtained in which self-dispersing carbon black B in which one C 6 H 3 — (COONH 4 ) 2 group was introduced on the surface of carbon black particles was dispersed in water.
• the self-dispersing carbon black B prepared above had an ionic group density of 3.1 ⁇ ⁇ ⁇ .
• the following compound (2) was dissolved in water to which sodium hydroxide had been added, and diazotization was performed by adding an aqueous sodium nitrite solution.
• the diazo turbid solution was dropped into an alkaline aqueous solution of 6-amino-1-hydroxynaphthalene-1,5-disulfonic acid to perform a force pulling reaction, salted out with sodium chloride, and then filtered and washed.
• the compound was dissolved in water added with sodium hydroxide, and diazotized by adding hydrochloric acid and sodium nitrite.
• 8-amino-11′hydroxynaphthalene-1,6-disulfonic acid and sodium carbonate were added and stirred overnight to obtain reaction solution A.
• 1-amino-2-benzenesulfonic acid was dissolved in water to which sodium hydroxide had been added, and a sodium nitrite aqueous solution was further added for diazotization.
• This diazo turbid solution is dropped into an alkaline aqueous solution of 6-amino-1-hydroxynaphthalene-1-sulfonic acid to effect a force pulling reaction. And salting out with sodium chloride, followed by filtration and washing.
• the compound was dissolved in water containing sodium hydroxide, and diazotized by adding hydrochloric acid and sodium nitrite. The diazo turbid solution was added to the reaction solution A, subjected to a force pulling reaction, salted out with sodium chloride, and then filtered and washed to obtain the following exemplified compound Bk1.
• the following compound (3) was dissolved in water to which sodium carbonate was added, and further dichlorinated by adding hydrochloric acid and sodium nitrite.
• 6_phenylamino- 1-hydroxynaphthalene-1-sulfonic acid aqueous solution was added and dissolved in the presence of sodium carbonate to obtain a solution B.
• 2-aminosulfonic acid is dissolved in the presence of sodium hydroxide, and hydrochloric acid and sodium nitrite are added! I kissed and did diazotization.
• 6-amino-1-hydroxynaphthalene-1-sulfonic acid was dissolved in the presence of sodium hydroxide, and acetic anhydride was added for acetylation.
• reaction solution C The diazo turbid solution obtained above was added dropwise in the presence of sodium carbonate to carry out a force pulling reaction to obtain reaction solution C.
• sodium hydroxide and then sodium chloride The compound was obtained by adding salt and salting out. This compound was dissolved in water in the presence of sodium hydroxide, and diazotized by adding hydrochloric acid and sodium nitrite.
• the solution B was dropped in the presence of sodium carbonate to complete the coupling reaction, thereby obtaining a reaction solution.
• the reaction solution was salted out with sodium chloride and then filtered to obtain Compound D.
• reaction solution was diazotized by adding hydrochloric acid and sodium nitrite, and the diazo turbid solution was added to the aqueous solution in which the compound D was dissolved to complete the coupling reaction. This was salted with sodium chloride, filtered, and washed to give Exemplified Compound B k 1. '
• Sulfolane, 4-sulfophthalic acid monosodium salt, ammonium chloride, silicon, ammonium molybdate, and copper (II) chloride were mixed and stirred, and then washed with methanol. Thereafter, water was added and the pH of the solution was adjusted to 11 using an aqueous sodium hydroxide solution. To the resulting solution was added an aqueous hydrochloric acid solution with stirring, and sodium chloride was gradually added to precipitate crystals. Resulting result The crystals separated by filtration were washed with 20 ° / 0 aqueous sodium chloride solution, followed by the addition of methanol.
• the precipitated crystals were separated by filtration, washed with a 70% aqueous methanol solution and then dried to obtain a copper phthalocyanine tetrasulfonic acid tetranato salt of compound (4) as blue crystals.
• the copper phthalocyanine tetrasulfonic acid tetrasodium salt (compound (4)) obtained above was gradually added to the throat sulfonic acid, and further thionyl chloride was added dropwise to carry out the reaction. Thereafter, the reaction liquid was cooled, and the precipitated crystals were filtered to obtain a wet cake of copper phthalocyanine tetrasulfonic acid chloride.
• Compound (6) is In the formula (V), the Y is Amino group, 1 ⁇ and 11 2 are substituted with a sulfonic acid group in 2 Kurai ⁇ Pi 5-position compound.
• Ink 10 is a compound corresponding to ink composition 2 in Patent Document 2 ⁇ Examples (7)
• the reactive inks 1 to 10 obtained above were filled in an ink cartridge for BJF 870 manufactured by Canon. Thereafter, the ink cartridge and the ink cartridge filled with the pigment ink were respectively mounted on a modified ink jet recording apparatus BJF 870 (manufactured by Canon).
• the ink jet recording apparatus the ejection opening for the pigment ink and the ejection opening for the reactive ink are the same. This is what is to be capped.
• the ink jet recording apparatus has a suction pump as a discharging means for removing the ink in the cap by depressurizing the inside of the cap, and the ink in the cap is removed by performing a suction operation. can do.
• the cap has a member that absorbs the ink therein.
• an A4 size recording medium (product name: office planner; manufactured by Canon) was used.
• the 10% duty of a solid image formed using the ink jet recording device BJF 87 0 is 6.0 0 01 1 6 '0 0 (4 It means to apply drops.
• the value of the mixed thickening ratio Y was determined as follows by combining the pigment ink and the reactive reactivity obtained above. First, the viscosity of the pigment ink and the reactive ink was measured. Then, the pigment ink and the reactive ink were mixed in the same volume and stirred for 30 minutes, and then the viscosity of the mixed ink was measured. From the viscosity value thus measured, the value of the mixed thickening rate was determined based on the following formula. The viscosity was measured using a V I S C ON I C E D type (manufactured by Tokyo Keiki Co., Ltd.) at a temperature of 25 ° C. Tables 2 and 5 show the values of the obtained mixed thickening rate.
• Viscosity ro / ol one viscosity of mixed ink Average viscosity of ink ⁇ and ink ⁇
• FIG. 7 shows the relationship between the mixing thickening rate and the distance between the discharge ports in the pigment links and the reactive links of Examples 1 to 4 and Comparative Examples 1 to 10. ''
• An image is formed by applying the pigment ink so as to have a duty of 150% and a reactive ink of 25% on the entire surface of the recording medium. It was.
• each ink was applied to the recording medium in the order of reactive ink and pigment ink.
• the pigment ink ejection port and the reactive ink ejection port were capped with the same cap and left for 6 hours.
• the nozzle check pattern of BJF 870 was recorded after performing the suction operation.
• Comparative Examples 1 to 4 and 8 to 10 the nozzle check pattern was recorded without performing the suction operation.
• the obtained nozzle check pattern was visually confirmed and evaluated.
• the evaluation criteria for reliability are as follows. Table 4 shows the evaluation results. .,
• the graph of FIG. 7 shows the relationship between the mixing thickening rate and the distance between the discharge ports in the pigment ink and reactive ink of L5.
• 4 0 1 indicates the relationship between the discharge port distance and the mixing thickening rate in Examples 1 and 5 and Comparative Example 1
• 4 0 2 indicates that in Examples 2 and 6 and Comparative Example 2 Points indicating the relationship between the discharge port distance and the mixing thickening rate
• an image was formed by applying the pigment ink so as to have a duty of 150% and a reactive ink having a duty of 25%.
• each ink was applied to the recording medium in the order of reactive ink and pigment ink. After that, a suction operation was performed, and the recording, recovery, and leaving cycle was repeated 10 times. Thereafter, a nozzle check pattern of B J F 870 was recorded. The obtained nozzle check pattern was visually confirmed and evaluated.
• the evaluation criteria for reliability are as follows. Table 5 shows the evaluation results. .
• an image (2) provided was formed.
• each ink was applied to the recording medium in the order of pigment ink and reactive ink.
• the obtained image was allowed to stand for one day, and the image density in the image (1) and the image (2) was visually confirmed and evaluated.
• the evaluation criteria for image quality are as follows. Table 5 shows the evaluation results.
• Image density of image (1) is higher than image density of image (2).
• Image density of image (1) is lower than image density of image (2).
• a recording pattern in which an image formed with a pigment ink and an image formed with a reactive ink were adjacent to each other was formed on the recording medium described above. Specifically, images were formed for characters and shorelines using a face-ink for 100% duty and for backgrounds a reactive ink for 50% duty. At this time, each ink was applied to the recording medium in the order of reactive ink and pigment ink. Evaluation was performed by visually confirming the degree of bleeding at the boundary of the obtained image.
• the evaluation criteria for bridging resistance are as follows. Table 5 shows the evaluation results.
• An image (2) imparted so as to become was formed.
• each ink was applied to the recording medium in the order of reactive ink and pigment ink.
• the color tone in the obtained image (1) and image (2) was visually confirmed and evaluated.
• the evaluation criteria for the color tone are as follows. Table 5 shows the evaluation results. '
• Reactive ink 4 was used as a weak reactive ink
• reactive ink 9 was used as a strong reactive ink.
• the distance between the discharge port of the pigment ink and the weak reactive ink was 1.7 mm
• the distance between the discharge port of the pigment ink and the strongly reactive ink was 16 mm.
• the ink jet recording device used was a modified BJF 870 (manufactured by Canon) similar to the above.
• the weak reactive ink ejection port and the pigment ink ejection port are capped with the same cap, and the strong reactive ink
• the nozzle outlet and pigment ink outlet were sealed with different caps.
• the same A4 size recording medium product name: office planner; manufactured by Canon
• each ink was applied to the recording medium by setting the ejection openings of each ink as follows.
• the discharge port for pigment ink is 31, the discharge port for weakly reactive ink is 32, and the discharge port for strong reactive ink is 33.
• the discharge port for weakly reactive ink is 34, the discharge port for pigment ink is 35, and the discharge port for strong reactive ink is 3 It was 6. '(Image quality)
• Example 19 to 22 described above the pigment-in was applied to the recording medium described above in an overlapping manner in the order shown in Table 6 so that the pigment-in was 1550% duty and each reactive ink was 25% duty.
• Each image (1) was formed.
• an image (2) was formed on the above-described recording medium by applying the pigment ink so as to overlap with 150% duty and reactive ink 3 with 25% duty. .
• each ink was given to the recording medium in the order of the facial ink and the “reactive ink 3” in the forward recording of the recording pass.
• Example 1 formed using two types of reactive inks Visually inspect the image density in images (1) and 9-2 (2) and images (2) formed using one type of reactive ink. And evaluated.
• the image quality evaluation criteria are as follows. Table 6 shows the evaluation results. '.
• Image density of image (1) is higher than image density of image (2).
• the image density of the image (1) is equal to the image density of the image '(2), or the image density of the image (1) is lower than the image density of the image (2).
• Four images were formed.
• an image (1) formed by applying each ink in the order of pigment ink, weakly reactive ink, and strongly reactive ink, and strongly reactive ink Weakly reactive images (2) formed by applying each ink in the order of ink and pigment ink were compared.
• the images (4) formed by assigning each ink in the order of pigment ink and weakly reactive ink were compared. Evaluation was performed by visually confirming reciprocal unevenness in each image obtained by forward recording and backward recording using a recording head having the configuration shown in FIG. 13 and FIG.
• the evaluation criteria for the round-trip unevenness are as follows. Table 7 shows the evaluation results.

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