Ink-jet printing apparatus

Abstract: Upon performing printing using a dye ink and a pigment ink and in addition a treatment liquid making those inks insoluble, two kinds of inks consisted of the pigment ink (I p ) and the dye ink (I d ) are used. After applying the pigment ink (I p ) on a printing medium (P), the dye ink (I d ) is applied overlaying with the pigment ink. After mixing these inks on the printing medium (P), the treatment liquid (S) which makes the inks insoluble, is applied. In the alternative, a mixed ink (I m ) in which a pigment ink not requiring a dispersant and the dye, is used. After application of this mixed ink (I m ) on the printing medium (P), the treatment liquid (S) which makes the ink (I m ) insoluble, is applied. Therefore, problem of "crack", "soaking out", "overflow" or lowering of OD value which can be caused upon reaction of the pigment ink (I p ) and the dye ink (I d ) or the mixed ink (I m ) with the treatment liquid (S), can be solved to achieve high quality printing.

Description: The present invention relates generally to an ink-jet printing apparatus and a printing method. More particularly, the invention relates to an ink-jet printing apparatus and a printing method performing printing of characters, images and the like on a printing medium, such as a printing paper, an OHP film and the like using an ink and a liquid which makes a coloring material in the ink insoluble or breaks its dispersion (hereinafter also referred to as a treatment liquid). A treatment liquid of this kind reacts with a coloring material contained in an ink, such as a pigment, dye and the like and makes the coloring material insoluble or breaks its dispersion. In the ink-jet printing technology, in general, the treatment liquid is ejected overlaying on the portion where the ink is ejected on the printing medium or in the vicinity thereof, for admixing the ink and the treatment liquid to cause reaction. Then, as a result of reaction, the coloring material of the ink is fixed on the surface of the printing medium or with penetrating into the printing medium for achieving water resistance of the printing product. It has also been known that action for making the coloring material in the ink insoluble also serves for limiting penetration of the pigment or dye in a surface layer of the printing medium, to result in improvement of an optical density of the printing medium (hereinafter occasionally simply referred to as "OD value"). However, in the conventional ink-jet printing technology using the foregoing treatment liquid, it has been newly recognized by the inventors that there have been respective problems per coloring materials to be employed in the ink for improving printing quality. When a dye is used as the coloring material, a first problem is encountered in that sufficiently high OD value cannot be obtained even when the dye and the treatment liquid are reacted. This is because that the dye per se cannot develop relatively high OD value as used for printing. Therefore, even if the treatment liquid and the dye are reacted to fix the most part of the dye in the surface layer of the printing medium as above-mentioned, the OD value is not so high as compared with the case where pigment is used as the coloring material. The second problem to be encountered in the dye that the inventor has found, is a phenomenon so-called "overflow" or "sweep", and particularly that an edge portion of a printed image becomes blur. Figs. 1A to 1D are illustrations for explaining the phenomenon in the predictive manner. As shown in Fig. 1A, when an ink I d using a dye as a color agent, is deposited on the lower penetrative printing medium P such as a plane paper by ejection of the ink through a printing head as an ejecting portion, a part of the ink penetrates into the printing medium and remaining part of the ink is present in a liquid state on the surface of the printing medium P. Then, as shown in Fig. 1B, in the similar manner, a treatment liquid S is deposited overlaying over the ink I d to cause reaction in a boundary between the treatment liquid S and the ink I d by ejection through the printing head. As shown in Fig. 1C, a part of a reaction product flows out to the circumference of the ink I d and flows into the lower side of the ink I d . Then, associating with progress of such phenomenon, a reaction between the dye in the ink I d and the treatment liquid S is gradually progressed. Finally, an ink dot consisted of the reaction product of the dye and the treatment liquid is formed as shown in Fig. 1D. The ink dot thus formed has a contour portion where the ink flows beyond the contour that the dot should have. According to prediction by the inventor, the foregoing phenomenon is caused by flow of a gel form high viscous reaction product in the ink and the treatment liquid for relatively low reaction speed between the dye and the treatment liquid. Flowing out of the ink in the ink dot shown in Fig. 1D due to such phenomenon makes the contour blur at the edge portion of an image, and appears as so-called "overflow" to cause degradation of the printing quality. Fluidizing of the foregoing reaction product also causes "sweep" of the reaction product in the direction of relative movement between a printing medium fed and the printing head for the treatment liquid. Even therefore, it has been predicted that the edge portion of the printed image becomes blur, similarly. The second problem concerning dye set forth above does not occur in the case where only dye ink is used and the treatment liquid is not used in printing. Accordingly, in the case where printing is performed using the dye ink and the treatment liquid which makes the dye ink insoluble, particular technical problem is encountered. Next, even if printing is performed using an ink including a pigment as the coloring material and the treatment liquid therefor, particular problem caused due to reaction between the ink and the treatment liquid will be explained hereinafter. The pigment ink per se exhibits relatively high OD value as used for printing. By reaction with the treatment liquid, owing to the effect of the treatment liquid set forth above, the OD value of the pigment ink can be improved. In comparison with the foregoing dye, the pigment has high reaction speed with the treatment liquid. However, as the first problem in the case where pigment is used, a problem of "crack" has been found by the inventors. Namely, when reaction of the pigment ink and the treatment liquid is caused especially on the film-like printing medium for an OHP, since reaction speed of the pigment with the treatment liquid is high as set forth above, most of the pigment is coagulated (its dispersion is broken) on the surface before penetration into the printing medium. Furthermore, owing to property of the pigment, the pigment may coagulate strongly. Therefore, after a solvent in the ink has penetrated into the printing medium and been fixed therein, the coagulated reaction product set forth above will become relatively large individual blocks due to coagulation force to form gaps not filled by the reaction product between these individual blocks. This phenomenon is perceived as "crack" upon observing visually to degrade quality of the printed image. When the foregoing reaction product is not filled, the surface of the printing medium is exposed to lower OD value of the overall printed image. In the pigment ink, there are an ink using a dispersant, such as a resin, a surface-active agent and the like, in order to stabilize dispersion of the pigment in the ink solvent (hereinafter occasionally referred to as dispersant containing pigment ink), and an ink using a self-dispersion type pigment and containing no dispersant (hereinafter occasionally referred to as no dispersant containing pigment ink). The second problem concerning the pigment ink is caused in the case where the latter no-dispersant-containing pigment ink and the treatment liquid are used. By the inventor, phenomenon called "soaking out" or "blur" is observed in a dot formed on the printing medium using the no dispersant containing pigment ink and the treatment liquid. Figs. 2A to 2C are illustrations for predictively explaining this phenomenon. After application of the no dispersant containing pigment ink I p on the printing medium P such as a plane paper (see Fig. 2A), the treatment liquids is applied in overlaying manner (see Fig. 2B). Then, production of reaction product is initiated, at first, at the boundary between the ink and the treatment liquid. Then, according to progress of this reaction, radial "soaking out" is caused from substantially circular dot of the reaction product to "blur" the entire circumference of the dot (see Fig. 2C). Such "soaking out" or "blur" appears similar to known feathering. Accordingly, printing quality is lowered. The foregoing "soaking out" or "blur" is inferred as the following phenomenon chemically or in micro view. The no dispersant containing pigment ink has relatively high reaction speed in reaction with the treatment liquid. Therefore, the dispersed pigment instantly cause dispersion breakage to generate cluster of the reaction product. In conjunction therewith, particulate reaction product is also generated. Then, the particulate reaction product flows out associating with penetration of the treatment liquid into the printing medium to result in the foregoing "soaking out". As set forth above, in either case of performing printing using the dye ink and the treatment liquid and performing printing using the pigment ink and the treatment ink, there have been problems newly recognized by the inventors, in improving the printing quality, to be solved. The use of an ink and a treatment liquid, in which the ink is a mixture of a dye ink and a pigment ink containing a dispersant is proposed in EP-A-0 724 968 and JP-A-8-267903. According to the present invention there is provided ink jet recording apparatus as set out in claim 1 and claim 8, and printing methods as set out in claim 26 and claim 33. The remaining claims set out optional features. In embodiments of the present invention which use an ink having both dye and a self-dispersion type pigment (referred to as a "mixed ink"), since the mixed ink and the treatment liquid are mixed on the printing medium, "crack" or "soaking out" which could be caused upon printing by using only the pigment ink and the treatment liquid, can be suppressed by the simultaneous presence of the mixed-in dye. Conversely, lowering of an OD value or "overflow" which could be caused upon printing by using only the dye ink and the treatment liquid, can be compensated, or suppressed by the simultaneous presence of the mixed-in pigment. Preferably the treatment liquid penetration speed is higher than or equal to 5.0 (ml/m 2 • msec 1/2 ) in Ka value by the Bristow method. Thus, in addition to the effect in the case where printing is performed by using the mixed ink and the treatment liquid, since the treatment liquid having relatively high penetration ability as the treatment liquid, the reaction product of the pigment or the like and the treatment liquid may also have high penetration ability to achieve high penetration speed as a whole. (First Practical Aspect) In a practical aspect of the present invention, the ink using the dye and the pigment with no dispersant as coloring materials (hereinafter referred to as mixed ink) is applied to the printing medium to form a dot of the reaction product by applying the treatment liquid. Figs. 3A to 3C are illustrations for explaining dot formation. As shown in Fig. 3A, at first, the mixed ink I m is applied to the printing medium. Then, as shown in Fig. 3B, the treatment liquid S is applied overlaying the mixed ink I m . Therefore, the reaction product generated by reaction of the mixed ink I m and the treatment liquid S is fixed on the surface and inside of the printing medium P to form the dot. According to the practical aspect, firstly, since the ink containing the dye and the pigment without dispersant is used for printing, lowering of OD value to be caused by the dye ink can be compensated by the pigment ink to enhance the OD value. Also, most of the reaction product of the ink as mixed with the treatment liquid may stay in an upper layer of the printing medium to contribute for increasing of the OD value. When the ink having low penetration speed is used as the mixed ink, even if an interval is provided before application of the treatment liquid to provide a relatively long period for penetration, the amount of the coloring material staying in the surface layer of the printing medium can be made large to further improve the OD value. In other words, when an ink is used in which the dye and the pigment having no dispersant are mixed, then even if the ink has a low penetration speedy the problems caused in using the dye ink and the pigment ink alone can be solved or reduced. By using the ink having further lower penetration speed, increasing of the OD value can be expected. Furthermore, as the effect of using of the ink having low penetration speed, so-called feathering can be suppressed. Next, the maximum effect of the practical aspect, in which the treatment liquid is applied after application the mixed ink on the printing medium, is to solve the problem of "overflow" or "sweep" to be caused by the dye ink and the problem of "soaking out" or "blur" to be caused by the pigment ink are solved or reduced simultaneously. By the inventors, the principle achieving these effects can be predicted as follow. After application of the mixed ink onto the printing medium, the treatment liquid is applied. Then, the dye and the treatment liquid are reacted to form a gel form high viscous substance. The pigment having no dispersant causes breakage of dispersion by reaction with the treatment liquid. It is considered that fine particle of the pigment generated by dispersion breakage is taken into the high viscous substance of the dye reaction product to restrict "soaking out" or "blur" which could be caused by flowing out of the pigment particle. The high viscous substance taking in the pigment particles has not so high flow ability in comparison with the reaction product of the dye alone and the treatment liquid. Accordingly, occurrence of "overflow" or "sweep" can be suppressed simultaneously. In the construction where the treatment liquid is applied to the mixture of the dye and the pigment having no dispersant, the fine particles of the pigment generated by dispersion breakage are taken into the gel form reaction product so as not to deeply penetrate into the printing medium and not to enter gaps between fibers of the printing medium in the surface layer. Then, the gel form dye reaction product fills gap between absorbed particles and unevenness of the fiber on the surface of the printing medium. Therefore, irregular reflection of the light can be presented to achieve OD value higher than that achieved when the pigment and the treatment liquid are used. According to the practical aspect, as diagrammatically shown in Fig. 3C, phenomenon to be a factor of degradation of the printing quality, such as "blur", "overflow" or the like, can be prevented. Furthermore, increasing of the OD value can be achieved. Phenomenon of "blur" or "overflow" tends to be caused by reaction of the pigment ink or the dye ink with the treatment liquid before penetration into the printing medium. Therefore, in order to suppress occurrence of these phenomena, it becomes necessary to apply the treatment liquid after waiting for penetration of the dye ink or the like which interferes with speeding up of the printing. However, in the practical aspect, since "blur" or the like can be suppressed by the mixed ink per se, which is a mixture of the dye and the pigment ink having no dispersant, it becomes unnecessary to allow an interval before application of the treatment liquid for penetration of the dye ink or the like into the printing medium. Accordingly, speeding up of the printing will not be interfered with. In other words, the OD value can be further improved by using the mixed ink of the practical aspect having relatively low penetration ability so that the coloring material, such as the pigment or the like may stay in the surface layer of the printing medium for a long period. In addition, in the ink-jet printing apparatus employing the full-multi type head, an interval from application of the mixed ink to application of the treatment liquid can be shortened and the speed of print for the first printing medium, called first print, can be increased. On the other hand, since the foregoing interval can be shortened, down-sizing of the apparatus and lowering of cost can be achieved. The order of application of the mixed ink and the treatment liquid onto the printing medium in the practical aspect is basically that the treatment liquid is applied after application of the mixed ink on the printing medium, as set forth above to attain the foregoing effect. As a particular construction allowing this order of application, when a serial type head is used, for example, a plurality of times of scan is performed for the same region with an interval for paper feeding, so that foregoing order is realized. While the mixed ink in the practical aspect is applied in advance of application of the treatment liquid, the amount of the mixed ink to be applied is not limited to one droplet as set forth above. For example, it may be possible to apply two droplets of the mixed ink in advance of application of the treatment liquid. In this case, preferably, among these two droplets, the mixed ink applied at earlier timing is contains greater proportion of dye than the pigment having no dispersant, and the mixed ink applied later timing contains greater proportion of pigment having no dispersant than the dye. Therefore, upon reaction with the treatment liquid applied later, greater proportion of pigment may react with the treatment liquid to further suppress flow out of the reaction product of the dye and the treatment liquid. As another practical aspect which can achieve equivalent effect, number of the mixed ink droplet to be applied in advance of application of the treatment liquid is set to three and proportions of the pigment having no dispersant are preferably increased in the mixed ink to be applied in later timing. When a plurality of mixed ink droplets are applied, total amount of the applied ink is set to be substantially equal to the case where one droplet is applied. In other words, according to the practical aspect of the present invention, when the mixed ink is applied with dividing into a plurality of droplets, even if the amount of the ink per droplet becomes smaller according to increasing of number of divided droplets, the foregoing effect can be attained. Any difference of timings of application of the mixed ink in the practical aspect and the treatment liquid may be encompassed within the scope of the present invention as long as respective effect of the practical aspect can be achieved, similarly to the order of application set forth above. Namely, depending upon a timing from application of the mixed ink to application of the treatment liquid, reaction between the mixed ink and the treatment liquid can be caused in various modes. For example, when the time is short, mixing of the mixed ink and the treatment liquid becomes insufficient. In the circumferential portion of the dot formed by overlaying the mixed ink and the treatment liquid, namely the edge portion, mixing of the pigment or the like and the treatment liquid can be done sufficiently to achieve respective effect of the practical aspect, particularly in suppression of "blur" or "overflow". Therefore, in this disclosure, "mix" of the mixed ink and the treatment liquid means not only wholly mixing but also partial mixing at the edge portion and so on. Furthermore, "mix" also represents mixing after penetration into the printing medium. Modes of all of these mixing will be defined as "mixing in liquid state". Color (kind), density and number of the ink applied in the practical aspect can be combined arbitrary as long as the foregoing order of application is maintained. For example, as the kind of the inks of black (Bk), yellow (Y), magenta (M) and cyan (C) inks are used generally. Concerning respective colors, high and low density inks may also be used. Further particularly, with taking at least one of yellow ink, magenta ink and cyan ink as mixed ink in the practical aspect, and using the treatment liquid, the mixed ink and the treatment liquid are applied in sequential order. Among such combinations, for which the present invention is applicable, the most preferred mode is to use the mixed ink as the black ink. According to this mode, respective effect of the practical aspect, such as increasing of the OD value, suppression of "blur" or "overflow" contributes for printing quality of the characters, such as letters or the like. As the method applying these mixed ink and so on to the printing medium, the most preferred mode is the ink-jet printing type employing a printing head. Then, in this case, combination and arrangement of the printing head as the ejecting portion is determined according to combination of application order and kinds of the ink including the treatment liquid. Particularly, by a construction, in which the heads for the mixed ink and the treatment liquid are arranged in a direction of relative movement of the printing head with respect to the printing medium, the foregoing sequential order of application becomes possible. As more particular construction, either case of so-called full-multi type printing head, in which the ink ejection openings are arranged within a range corresponding to the entire width of the printing region in the printing medium or serial type printing head performing movement for scanning relative to the printing medium may permit application of the ink and the treatment liquid. In the ink ejection system of the printing head, any known type, such as piezo type or the like can be employed. Most preferred mode is to generate bubble in the ink or the treatment liquid utilizing thermal energy to eject the ink or the treatment liquid by the pressure of the bubble. Furthermore, by each printing head, a range where the mixed ink and the treatment liquid are ejected to overlay, is normally controlled per pixel forming the printed image or so on. The foregoing ink or the like are ejected at the same position in overlaying manner. However, application of the present invention is not limited to the foregoing construction. For example, a construction, in which a part of the dot of the mixed ink and the treatment liquid are overlaid to achieve the predetermined effect of the practical aspect or a construction, in which the treatment liquid is applied for data of respective pixels with thinning to cause reaction between the treatment liquid and the pigment or the like flowing from adjacent pixel by bleeding or the like, may be provided. (Second Practical Aspect) Another practical aspect of the present invention will be explained. The practical aspect is intended to achieve high speed fixing by employing the treatment liquid having high penetration ability as the treatment liquid in the practical aspect. High speed fixing is a major factor for achieving speeding up of the printing speed, namely for improvement of throughput. By increasing a driving frequency of the printing head or transporting speed of the printing medium, direct improvement of throughput becomes possible. However, when the ink or the like on the printing medium discharged after printing is not yet fixed, inconvenience can be caused in subsequent handling. Also, in a construction where the discharged printing media are stacked, non-fixed ink may cause stain of other printing medium. Namely, among various factors contributing for speeding up of the printing speed, a major factor is a discharge speed of the printing medium after completion of printing, which depends on feeding speed of the printing medium or scanning speed of the printing head. Namely, in the printing apparatus employing the full-multi type printing head, the feeding speed of the printing medium in printing operation directly corresponds to the discharge speed. In the printing apparatus employing the serial type printing head, the scanning speed is directly associated with the discharge speed of the printing medium after completion of printing. Then, the feeding speed of the printing medium and so on is correlated to the ink ejection period for the pixel via resolution of printing, namely via dot density. Therefore, in the construction performing printing of one pixel by the ink ejected from a plurality of printing head, when the resolution is considered to be fixed, the ejection period and the feeding speed and so on with respect to the pixel is correlated. In consideration of respective technical tasks relating to reaction of the dye ink and the pigment ink with the treatment liquid, it is preferred to make the period from ink ejection to ejection of the treatment liquid as long as possible. The reason is that, when the dye ink or the pigment ink reacts with the treatment liquid after penetration into the printing medium, the foregoing problem phenomena will be hardly caused. In other words, when printing is performed using the dye ink, the pigment ink and the treatment liquid therefor, the foregoing problems also interfere with speeding up of the printing. Particularly, when the dye ink and the pigment ink having low penetration speed is used for achieving improvement of the OD value, the difficulty in speeding up becomes particularly significant. In the practical aspect, after application of the mixed ink on the printing medium, by applying the treatment liquid having high penetration speed, respective effect set forth in the first practical aspect can be caused. Even if the mixed ink having relatively low penetration speed is used, the penetration speed is increased associating therewith. Namely, when the penetration speeds of the mixed ink and the treatment liquid with respect to the printing medium are v 1 and v 2 respectively, v 1 < v 2 is satisfied. In Fig. 4, phenomenon is shown predictively. Fig. 4 shows the case where the mixed ink I m and the treatment liquid S are applied to the printing medium P in the sequential order. In this case, reaction product starts to be generated between the treatment liquid S and the mixed ink I m contacting at the boundary. The penetration speed of the mixture between the treatment liquid S and the mixed ink becomes higher than that of the case where the mixed ink is used alone. Thus, as a whole, by speeding up of the penetration to be higher than that in the mixed ink alone, high speed fixing becomes possible. In the practical aspect, by using the treatment liquid having high penetration speed, particularly when the mixed ink having low penetration speed is used for improving the OD value or the like, relatively high speed fixing can be achieved. (Third Practical Aspect) Still further practical aspect of the present invention relates to order of application of the mixed ink and the treatment liquid. Namely, in the practical aspect, after application of the mixed ink, the treatment liquid is applied, and thereafter, the mixed ink is further applied. The practical aspect is particularly effective in improvement of OD value, restriction of "overflow", "blur" or feathering among the foregoing effects. Using the treatment liquid having high penetration ability as the treatment liquid to be applied between application of the mixed ink, relatively high fixing ability can be obtained. It is considered that the foregoing function and effect of the practical aspect is achieved because less fluidization is caused in reaction between the initially applied mixed ink and the treatment liquid because of the relatively small amount of the mixed ink, and when the mixed ink is applied after application of the treatment liquid, since increase of viscosity due to reaction between the initially applied mixed ink and the treatment liquid has progressed to certain extent and penetration of the ink and so on has also progressed to a certain extent, flow ability is lower. In case of the practical aspect, the ink to be applied after application of the treatment liquid is preferred to be the mixed ink set forth above, but can be a self-dispersion type pigment ink or the dye ink. In embodiments of the present invention which use a pigment ink and a dye ink since the pigment ink, the dye ink and the treatment liquid are mixed on the printing medium, "crack" or "soaking out" which could be caused upon printing using the pigment ink and the treatment liquid, can be reduced by the presence of the dye ink. Conversely, lowering of the OD value or "overflow" which could be caused upon printing using only the dye ink and the treatment liquid can be compensated or reduced by the presence of the pigment ink. Preferably, the treatment liquid penetration speed is higher than or equal to 5.0 (ml/m 2 • msec 1/2 ) in Ka value by the Bristow method. Upon printing with mixing the dye ink, the pigment ink and the treatment liquid, in addition to the foregoing function, since the treatment liquid having relatively high penetration ability is used, the reaction product of the pigment ink or the like and the treatment liquid also has high penetration ability to speed up penetration speed as a whole. (Fourth Practical Aspect) In the practical aspect of the present invention, the dye ink and the pigment ink are mixed on the printing medium, and the treatment liquid is applied to the mixture of the dye ink and the pigment ink to form a dot by the reaction product. Figs. 5A to 5D are illustration for explaining formation of dot. As shown in Fig. 5A, at first, the dye ink I d is applied to the printing medium. Then, as shown in Fig. 5B, the pigment ink I p is applied overlaying the dye ink I d . Also, as shown in Fig. 5C, to the liquid, in which the dye ink I d and the pigment ink I p are mixed, the treatment liquid S is applied. Therefore, the reaction product generated by reaction of the mixture liquid of the inks and the treatment liquid S is fixed on the surface and inside of the printing medium P to form the dot, as shown in Fig. 5D. According to the practical aspect, at first, the dye ink and the pigment ink are mixed on the printing medium, and mixed ink is used for printing. Therefore, lowering of the OD value caused by printing by the dye ink can be compensated by the pigment to enhance the OD value. Furthermore, the reaction product of the treatment liquid and the mixed ink stays in the upper layer portion of the printing medium in large proportion to increase the OD value. When the dye ink and the pigment ink having low penetration speed are used, if the period before application of the treatment liquid is long to provide a long period for penetration, large proportion of the coloring material may stay in the surface layer of the printing medium to enhance the OD value. In other words, by the effect of using both of the dye ink and the pigment ink explained later, even if the ink having low penetration speed is used, the problems caused when the dye ink and the pigment ink are used alone, can be solved or reduced. Therefore, the dye ink or the pigment ink having further lower penetration speed can be used. Thus, further increasing of the OD value can be expected. Furthermore, as a effect of using of the ink having low penetration speed, so-called feathering can be restricted. Secondly, in addition to the effect of improvement of the OD value set forth above, as the effect of printing by mixing the dye ink and the pigment ink on the printing medium, the problem of "crack" can be solved or reduced. When the printing medium, such as plain paper or the like is used, the dye ink and the pigment ink are mixed on the printing medium, and subsequently, the treatment liquid is applied. The pigment may react with the treatment liquid to coagulate (break its dispersion) to generate block of the reaction product. In mutual gap between a plurality of blocks thus generated, the reaction product of the dye reacted with the treatment liquid is fluidized to penetrate therein for fill. Therefore, occurrence of so-called "crack" set forth above can be prevented and restricted. As the third effect of the practical aspect, in which the dye ink and the pigment ink are mixed on the printing medium and the treatment liquid is applied to the mixed inks, problem of "overflow" or "sweep" could by caused in printing by the dye ink and the problem of "soaking out" or "blur" could be caused upon printing by the pigment ink containing no dispersant can be solved or reduced simultaneously. By the inventors, the principle achieving these effect can be predicted as follow. Namely, after the mixing of the inks on the printing medium, the treatment liquid is applied. Then, the dye and the treatment liquid are reacted to form a gel form high viscous substance. The pigment having no dispersant causes breakage of dispersion by reaction with the treatment liquid. It is considered that fine particle of the pigment generated by dispersion breakage are taken into the high viscous substance of the dye reaction product to restrict "soaking out" or "blur" which could be caused by flowing out of the pigment particles. The high viscous substance absorbing the pigment particle has not so high flow ability in comparison with the reaction product of the dye alone and the treatment liquid. Accordingly, occurrence of "overflow" or "sweep" can be suppressed simultaneously. In the construction where the treatment liquid is applied to the mixture of the dye and the pigment having no dispersant, the fine particles of the pigment generated by dispersion breakage are taken into the gel form reaction product so as not to deeply penetrate into the printing medium and not to enter gaps between fibers of the printing medium in the surface layer. Then, the gel form dye reaction product fills gap between absorbed particles and unevenness of the fiber on the surface of the printing medium. Therefore, irregular reflection of the light can be presented to achieve OD value higher than that achieved when the pigment and the treatment liquid are used. According to the practical aspect, as diagrammatically illustrated in Fig. 5D, in conjunction with restriction of occurrence of phenomenon, such as "blur" or "overflow" which could be factor for degradation of printing quality, effect of increasing of the OD value and "crack" can be achieved as set forth as the foregoing first and second effects. The phenomenon of "blur" or "overflow" can be caused by reacting the pigment ink or the dye ink with the treatment liquid before penetration into the printing medium. Therefore, in order to suppress occurrence of these phenomena, it becomes necessary to apply the treatment liquid after waiting for penetration of the dye ink or the like, which interferes with speeding up of the printing. However, in case of the practical aspect, since "blur" or the like can be suppressed by the mixed ink per se, which is a mixture of the dye and the pigment ink having no dispersant, it becomes unnecessary to allow an interval before application of the treatment liquid for penetration of the dye ink or the like into the printing medium. Accordingly, speeding up of the printing will not be interfered with. In other words, the OD value can be further improved by using the mixed ink of the practical aspect having relatively low penetration ability so that the coloring material, such as the pigment or the like may stay in the surface layer of the printing medium for a long period. In addition, in the ink-jet printing apparatus employing the full-multi type head, an interval from application of the mixed ink to application of the treatment liquid can be shortened and the speed of print for the first printing medium, called first print, can be increased. Since the foregoing interval can be shortened, down-sizing of the apparatus and lowering of cost can be achieved. The order of application of the mixed ink and the treatment liquid onto the printing medium in the practical aspect is basically that the treatment liquid is applied after application of the mixed ink on the printing medium, as set forth above to attain the foregoing effect. According to study made by the inventors, among the foregoing order of application, it has been appreciated that the sequential order of the pigment ink, the dye ink and the treatment liquid or the sequential order of dye ink, the pigment ink and the treatment liquid are preferred. This is because that the effect of mixing in the practical aspect is most significant when the dye ink and the pigment ink are mixed in certain extent and thereafter reaction is caused with the treatment liquid. Among two sequential orders set forth above, when the pigment ink, the dye ink and the treatment liquid are applied in this order, in addition to the effect of the practical aspect set forth above, the effect of restricting so-called strike through can be achieved. Namely, deeper penetration of the coloring material of the dye or the like into the printing medium, so-called strike through such that a dot formed by this coloring material is noticeable from the back side of the printing medium, can be caused. However, in the sequential order of application set forth above, substantially no strike through can be observed. The reason is supposed that since the pigment applied at earlier timing has relatively large particles in the reaction product with the treatment liquid, the reaction product may be clogged in the gap between the fiber or the like of the printing medium to be impossible to penetrate any further. In the sequential order of application of the dye ink, the pigment ink and the treatment liquid, "overflow" or the like which could be caused using the dye ink and the treatment liquid, is hardly caused. Any difference of timings of application of the mixed ink in the practical aspect and the treatment liquid may be encompassed within the scope of the present invention as long as respective effect of the practical aspect can be achieved, similarly to the order of application set forth above. For example, timing difference of application of the pigment ink and the dye ink can be zero. Namely, the pigment ink and the dye ink may be applied to the printing medium simultaneously. Also, an interval from application of the pigment ink or the like to application of the treatment liquid is desired to include a time for mixing the pigment ink and the dye ink in order to obtain respective effect of the practical aspect set forth above. However, even in a period shorter than the foregoing interval, in the peripheral portion of the dot formed by overlaying the pigment ink and the like, namely the edge portion, sufficient mixing of the pigment and the like can be caused to achieve the effects of the practical aspect. Particularly, at least the effect of suppression of "blur" or "overflow" can be achieved. Color (kind), density and number of the ink applied in the practical aspect can be combined arbitrary as long as the foregoing order of application is maintained. For example, as the kind of the inks of black (Bk), yellow (Y), magenta (M) and cyan (C) inks are used generally. Concerning respective colors, high and low density inks may also be used. Further particularly, with taking at least one of yellow ink, magenta ink and cyan ink as mixed ink in the practical aspect, and using the treatment liquid, the mixed ink and the treatment liquid are applied in sequential order. Among such combinations, for which the present invention is applicable, the most preferred mode is to use the mixed ink as the black ink. With this mode, respective effect of the practical aspect, such as increasing of the OD value, suppression of "blur" or "overflow" contributes for printing quality of the characters, such as letters or the like. In the foregoing explanation, the pigment ink and the dye ink have been explained as those containing only pigment and only dye as coloring material components, respectively. The various effects set forth above can be achieved not only by the inks set forth above but also by the pigment ink partly containing the dye or the dye ink partly containing pigment. This the true even for the following explanation. Therefore, in this disclosure, as the coloring material, the ink containing the pigment only or the ink containing the pigment partly containing the dye are defined as "pigment ink containing the pigment as primary coloring material". Also, the ink containing the dye only or the ink containing the dye partly containing the pigment are defined as "dye ink containing the dye as primary coloring material". As the method applying these mixed ink and so on to the printing medium, various method, such as application or directly contacting the ink or the like to the printing medium for application and so on may be encompassed within the scope of the present invention. The most preferred mode is the ink-jet printing type employing a printing head. Then, in this case, combination and arrangement of the printing head as the ejecting portion is determined according to combination of application order and kinds of the ink including the treatment liquid. Particularly, by a construction, in which the heads for the mixed ink and the treatment liquid are arranged in a direction of relative movement of the printing head with respect to the printing medium, the foregoing sequential order of application becomes possible. Furthermore, by each printing head, a range where the pigment ink, the dye ink and the treatment liquid are ejected to overlay, is normally controlled per pixel forming the printed image or so on. The foregoing ink or the like are ejected at the same position in overlaying manner. However, application of the present invention is not limited to the foregoing construction. For example, a construction, in which a part of the dot of the pigment ink, the dye ink and the treatment liquid are overlaid to achieve the predetermined effect of the practical aspect or a construction, in which the treatment liquid is applied for data of respective pixels with thinning to cause reaction between the treatment liquid and the pigment or the like flowing from adjacent pixel by bleeding or the like, are included. (Fifth Practical Aspect) In the practical aspect, applying the treatment liquid having high penetration speed after application of the dye ink and the pigment ink onto the printing medium, the effect explained in the fourth practical aspect can be achieved. Also, even if the dye ink and the pigment ink having relatively low penetration speed is used, penetration speed can be made higher. Namely, penetration speeds of the pigment ink, the dye ink and the treatment liquid relative to the printing medium being v 1 < v 3 and v 2 < v 3 assuming that the penetration speed of the pigment ink is v 1 , the penetration speed of the dye ink is v 2 and the penetration speed of the treatment liquid is v 3 . Fig. 6 shows the case where the pigment ink I p , the dye ink I d and the treatment liquid S are applied on the printing medium P in the sequential order, and shows a condition where the treatment liquid S is applied at a timing where the pigment ink I p and the dye ink I d are not mixed sufficiently. In this case, the reaction product is generated at the boundary where the treatment liquid S and the dye ink I d contact. At first, since the penetration speed of the treatment liquid S is high, the reaction product may penetrate at higher speed than that when the dye ink is used alone. Since reaction between the dye and the treatment liquid per se is relatively low, the treatment liquid S further penetrates during reaction to also react with the pigment ink I p to make the penetration speed of the reaction product higher. Thus, as a whole, speed can be higher than the penetration speed of the case where the pigment ink and the dye ink are used alone, to permit high speed fixing. In the practical aspect, by using the treatment liquid having high penetration speed, even if the pigment ink and the dye ink having low penetration speed is used for improvement of the OD value and so on, fixing at relatively high speed becomes possible. (Sixth Practical Aspect) Further practical aspect of the present invention concerns order of application of one of the pigment ink, the dye ink and the treatment liquid. Namely, after application of the dye ink or the pigment ink, the treatment liquid is applied, and subsequently, the other of the pigment ink and the dye ink is applied. More particularly, application is performed in the order of the dye ink, the treatment liquid and then the pigment ink, or in the order of the pigment ink, the treatment ink and then the dye ink. According to this practical aspect, in comparison with the practical aspect, in which the treatment liquid is applied after application of both of the pigment ink and the dye ink, flow ability of the reaction product generated by reaction between the ink and the treatment liquid becomes lower to be advantageous in prevention of "overflow" and "sweep". According to an aspect of the present invention, since the pigment ink, the dye ink and the treatment liquid are mixed on the printing medium, "crack" or "soaking out" which could be caused when printing is performed only by the pigment ink and the treatment liquid can be reduced by presence of the dye ink simultaneously mixed. Conversely, lowering of the OD value or "overflow" which could be caused when printing is performed only by the dye and the treatment liquid, can be compensated by presence of the pigment ink simultaneously mixed and thus can be reduced. As a result, high quality printing can be performed with high OD value and avoiding "crack", "soaking out", "overflow" and so on. In addition to the effect to be achieved by printing with mixing the pigment ink and the treatment liquid, since the treatment liquid having relatively high penetration ability is used, the reaction product of the pigment ink and the treatment liquid may have high penetration ability to make the penetration speed high as a whole. As a result, fixing speed can be made higher to enable high speed printing. Embodiments of the present invention will be described in conjunction with the accompanying drawings. Figs. 1A to 1D are illustrations for predictively explaining "overflow" phenomenon of reaction product upon reaction of a dye ink and a treatment liquid therefor; Figs. 2A to 2C are illustrations for predictively explaining "soaking out" phenomenon of reaction product upon reaction of a pigment ink and a treatment liquid therefor; Figs. 3A to 3C are illustrations for predictively explaining dot formation upon reaction with the treatment liquid after application of an ink, in which both of a no dispersant containing pigment and a dye are mixed, in one practical aspect of the present invention; Fig. 4 is an illustration for explaining reaction and penetration with a mixed ink when a high penetrative treatment liquid is used as the treatment liquid in another practical aspect of the present invention; Figs. 5A to 5D are illustrations for predictively explaining reaction with the treatment liquid after mixing of the pigment ink and the dye ink on the printing medium in other practical aspect of the present invention; Fig. 6 is an illustration for explaining reaction and penetration with the pigment ink and the dye ink when high penetrative treatment liquid is used as the treatment liquid, in a further practical aspect of the present invention; Fig. 7 is a side elevation showing a general construction of one embodiment of a printing apparatus according to the present invention; Fig. 8 is a block diagram showing a construction of a control system of the printing apparatus shown in Fig. 7; Fig. 9 is a diagrammatic illustration showing a relationship between acetylenol content and a Ka value indicative of a penetration speed; Figs. 10A and 10B are characteristic charts each showing relationship between ink penetration amount and elapsed period; Fig. 11 is a perspective view showing a construction of another embodiment of the printing apparatus according to the present invention; Figs. 12A to 12C are diagrammatic illustration showing a head construction of a further embodiment of the printing apparatus according to the present invention; Fig. 13 is a perspective view showing a construction of a still further embodiment of the printing apparatus according to the present invention; Figs. 14A to 14C are graphs showing relationship between a ratio of pigment and printing ability; Figs. 15A to 15D are diagrammatic illustrations showing respectively anionic self-dispersion type pigment, anionic dye, cationic surface active agent, and cationic high polymer; Fig. 16 is a diagrammatic illustration showing reaction mode at a boundary portion between two anionic self-dispersion type pigment particles and intervening cationic high polymer; Fig. 17 is a diagrammatic illustration showing reaction mode at a boundary portion between two anionic self-dispersion type pigment particles and intervening anionic dye and cationic high polymer; and Fig. 18 is a diagrammatic illustration showing reaction mode at a boundary portion between two anionic self-dispersion type pigment particles and intervening anionic dye, cationic surface active agent and cationic high polymer. Particular embodiments of the foregoing practical aspects will be explained hereinafter with reference to the drawings. (First Embodiment) Fig. 7 is a side elevation showing a general construction of a full-line type printing apparatus according to one embodiment of the present invention. A shown printing apparatus 1 of ink-jet printing type performs printing by ejecting an ink and a treatment liquid by a plurality of full-line type printing heads as an ejecting portion arranged at predetermined positions along a feeding direction of a printing medium (a direction of arrow A in Fig. 1). The shown printing apparatus 1 is operated under control by a control circuit shown in Fig. 8, which will be explained later. Respective printing heads 101Bk1, 101Bk2, 101S, 101C, 101M and 101Y of a head group 101g can perform printing for a printing paper of maximum A3 size by arranging about 7200 ink ejection openings in a width direction (perpendicular direction of the paper surface of Fig. 7) of the printing paper fed in the direction A in Fig. 7. The printing paper 103 is fed in the direction A by rotation of a pair of registration rollers 114 which are driven by a motor for feeding. Then, a tip end of the printing paper 103 is registered as guided by a pair of guide plates 115. Thereafter, the printing paper 103 is fed by a feeding belt 111. The feeding belt 111 as an endless belt is held by two rollers 112 and 113. Deflection of the upper side portion of the feeding belt 111 in vertical direction is restricted by a platen 104. By driving the roller 113 for rotation, the printing paper 103 is fed. Attraction of the printing paper 103 onto the feeding belt 111 is performed by electrostatic suction. The roller 113 is driven to rotate by a driving source, such as a motor for rotation to feed the printing paper 103 in the direction of arrow A. While the printing paper 103 is fed on the feeding belt 111, the printing paper 103 printed by the printing head group 101g is ejected on a stacker 116. Each printing head of the printing head group 101g consists of two heads 101Bk1 and 101Bk2 ejecting the mixture ink of black color as set forth in the foregoing practical aspect, a head 101S for a treatment liquid ejecting the treatment liquid, heads for color inks (cyan head 101C, magenta head 101M, yellow head 101Y), arranged as shown along the feeding direction A of the printing paper 102. Then, by ejecting the respective ink and the treatment liquid through the printing head, character of black or color image can be printed. Fig. 8 is a block diagram showing a construction of a control system in the full-line type printing apparatus 1 shown in Fig. 7. A system controller 201 has a microprocessor, ROM storing a control program to be executed by the shown apparatus, RAM to be used as a work area performing a process of the microprocessor, and so on, for performing control of the overall apparatus. A motor 204 is controlled for driving thereof via a driver 202 and driven to rotate the roller 113 shown in Fig. 7 to feed the printing paper. A host computer 206 supplies information to be printed by this embodiment of the printing apparatus 1 to control printing operation. A reception buffer 207 temporarily stores data from the host computer 206 for accumulating data until data is read in by the system controller 201. A frame memory 208 is for developing data to be printed into the image data and has a memory size necessary for printing. In this embodiment the frame memory 208 is designed for storing one sheet of printing paper. However, the present invention should not be limited by memory capacity. The buffers 209S and 209P temporarily store data to be printed and have a storage capacity depending upon number of ejection openings of the printing head. A print control portion 210 is designed for appropriately control driving of the printing head by a command from the system controller 201, for controlling a driving frequency, a numbers of printing data and so on. The print control portion 210 also makes data for ejecting the treatment liquid. A driver 211 performs driving of the printing head 101S for ejecting the treatment liquid, printing heads 101BK1, 101Bk2, 101C, 101M and 101Y for respectively ejecting ink, and is controlled by a signal from the print control portion 210. The print data from the host computer 206 is transferred to and temporarily stored in the reception buffer 207. Next, the stored print data is read out by the system controller 201 and is developed in the buffers 209S and 209P. Plugging, running out of the ink, out of paper and so on can be detected by various detection signal from an abnormality detecting sensor 222. The print control portion 210 performs generation of data for treatment liquid in order to eject the treatment liquid on the basis of the image data developed in the buffers 209S and 209P. Then, on the basis of the print data and the treatment liquid data in respective buffers 209S and 209P, ejection operation of respective printing head is controlled. In the shown embodiment, concerning mixed ink of black ejected from the heads 101Bk1 and 101Bk2, an ink having low penetration speed (hereinafter referred to as low penetrative ink) is used. The treatment liquid and respective inks of cyan, magenta and yellow to be ejected through respective printing heads 101S, 101C, 101M and 101Y are the treatment liquid and the inks having high penetration speed (hereinafter referred to as high penetrative ink in the this embodiment). Here, penetration speed will be briefly explained hereinafter. Expressing penetration ability of the ink by an ink amount V per m 2 , for example, it has been known that an ink penetration amount (unit: ml/m 2 = µm) in a period t from ejection of the ink droplet is expressed by the following Bristow formula: V = Vr + Ka ( t - tw) 1/2 wherein Lt > tw Immediately after deposition of the ink droplet on the surface of the printing paper, the ink droplet is mostly accommodated in uneven portion of the surface of the printing paper, namely roughness portion of the surface of the printing paper and little amount of the ink is penetrated into the printing paper. This period is a period tw (contact time) and an amount to be accommodated in the uneven portion of the surface of the printing paper is indicated by character Vr. When the elapsed time after deposition of the ink droplet onto the surface of the printing paper exceeds the wet time tw, the penetration amount V is increased in an amount proportional to (1/2)th power (square root) of the additional period (t - tw). Ka is a proportional coefficient of the amount of increase and becomes a value corresponding to the penetration speed. Fig. 9 is an illustration showing a value of the proportional coefficient Ka with respect to a content of ethylene oxide-2,4,7,9-tetramethyl-5-decyne-4,7-diol (hereinafter referred to as acetylenol: tradename, available from Kawaken Fine Chemical) in the ink, obtained through experiments. Ka value was measured by means of a dynamic penetration testing device S (made by Toyo Seiki Seisakusho). In this experiments, a PB paper (tradename) as a plain paper available from Canon Kabushiki Kaisha as applicant of the present invention has been used. The PB paper is a printing paper to be used in an electrophotographic type copy machine, a laser beam printer (LBP) and an ink-jet printing type printer. Also, for a PPC sheet as a paper for electrophotography available from Canon Kabushiki Kaisha, similar result could be obtained. A curve shown in Fig. 9 is a curve of increasing Ka value (vertical axis) according to increasing of acetylenol content (horizontal axis). As can be appreciated from this, the proportional coefficient Ka is determined depending upon content of acetylenol. Therefore, penetration speed of the ink is determined substantially depending upon the content of the acetylenol. Lines parallel to the vertical axis and intersecting with the curve represent ranges of fluctuation of the measurement result. Figs. 10A and 10B are characteristic charts showing a relationship between the ink penetration amount and the elapsed time, in which are shown results of experiments performed using a printing paper of 64 g/m 2 , of thickness about 80 µm and of void fraction about 50%. In Fig. 10A, the horizontal axis represents (1/2)th power of the elapsed time t (msec 1/2 ), and in Fig. 10B, the horizontal axis represents the elapsed time t (msec). In both figures, the vertical axes represent penetration amount V (µm). In Figs. 10A and 10B, curves of the cases of acetylenol contents of 0%, 0.35% and 1% are shown, respectively. As can be clear from Figs. 10A and 10B, the penetration amount of the ink relative to the elapsed period becomes greater at greater content of the acetylenol. In the graphs shown in Figs. 10A and 10B, there are illustrated tendencies that the wet time tw becomes shorter at greater content of acetylenol and ink penetration ability becomes higher at greater content of acetylenol. When acetylenol is not mixed in an ink, namely acetylenol content is 0%, ink penetration ability is low to have a property as low penetrative ink which will be defined later. When acetylenol is mixed in the content of 1%, the ink has a property to be penetrated into the printing paper in a short period, and has a property as high penetrative ink. Then, the ink, in which acetylenol is mixed in the content of 0.35 %, has a property of semi-penetrative ink between the low penetrative ink and the high penetrative ink. Properties of the foregoing low penetrative ink, the high penetrative ink and the semi-penetrative ink therebetween are shown in the following table 1. Ka Value (ml/m 2 • msec 1/2 ) Acetylenol Content (%) Surface Tension (dyne/cm) Low penetrative ink < 1.0 < 0.2 40 ≦ Semi-Penetrative Ink 1.0 ≦ < 5.0 0.2 ≦ < 0.7 35 ≦ < 40 High Penetrative Ink 5.0 ≦ 0.7 ≦ < 35 The foregoing table 1 shows Ka value, acetylenol content (%) and surface tension (dyne/cm) of respective low penetrative ink, the semi-penetrative ink and high penetrative ink, respectively. The penetration ability of respective ink for the printing paper as the printing medium becomes higher at greater Ka value. Namely, the penetration ability of the ink becomes higher at smaller surface tension. In the table 1, the Ka value has been measured by the dynamic penetration test device S (made by Toyo Seiki Seisakusho) of the liquid by the foregoing-Bristow method). In the experiments, the PB paper available from Canon Kabushiki Kaisha as applicant of the present invention has been used. Also, for the PPC paper as a paper for electrophotography available from Canon Kabushiki Kaisha, similar result could be obtained. Here, as a condition in the case where the surface-active agent is contained in certain liquid, it has been known that there is a critical micell concentration (CMC) of the surface-active agent in the liquid. The critical micell concentration represents the concentration at which, when the concentration of a solution of the surface-active agent is increasing, several tens of molecules suddenly gather to form a micell. Acetylenol, used for adjustment of penetration of the ink set forth above, is a kind of surface-active agent. For acetylenol, the critical micell concentration depends upon the liquid. As a relationship with the surface tension in the case where acetylenol content is adjusted, there is a relationship that when micell is formed, the surface tension may not be lowered. Thus, it has been confirmed that CMC of acetylenol with respect to water is about 0.7%. Making the critical micell concentration shown in Figs. 10A and 10B corresponded to the foregoing table 1, for example, the high penetrative ink defined in the foregoing table 1 is appreciated as the ink containing acetylenol at a higher content than that of CMC of acetylenol in water. Compositions of the treatment liquid and respective inks to be used in this embodiment are as follows: [Treatment Liquid] glycerin 7 Wt.% diethylene glycol 5 Wt.% acetylenol EH (made by Kawaken Fine Chemical) 0.7 Wt.% polyarylamine (molecular weight: 1500 for less, average molecular weight: about 1000) 4 Wt.% ethanoic acid 4 Wt.% Benzalkonium chloride 0.5 Wt.% triethylene glycol monobutylether 3 Wt.% water remainder [Yellow (Y) Ink] C. I. direct yellow 86 3 Wt.% glycerin 5 Wt.% diethylene glycol 5 Wt.% acetylenol EH (made by Kawaken Fine Chemical) 1 Wt.% water remainder [Magenta (M) Ink] C. I. direct acid red 289 3 Wt.% glycerin 5 Wt.% diethylene glycol 5 Wt.% acetylenol EH (made by Kawaken Fine Chemical) 1 Wt.% water remainder [Cyan (C) Ink] C. I. direct blue 199 3 Wt.% glycerin 5 Wt.% diethylene glycol 5 Wt.% acetylenol EH (Kawaken Fine Chemical) 1 Wt.% water remainder [Mixed Ink of Black (Bk)] pigment dispersion liquid 25 Wt.% food black 2 2 Wt.% glycerin 6 Wt.% trietylene glycol 5 Wt.% acetylenol EH (made by Kawaken Fine Chemical) 0.1 Wt.% water remainder The Ka value of this mixed ink of black is 0.33. The above pigment dispersion liquid is as follow. [Pigment Dispersion Liquid] In a solution prepared by mixing 5g of concentrated hydrochloric acid in 5.3g of water, 1.58g of anthranilic acid was added at a temperature of 5 °C. The solution was stirred in an ice bath to be constantly maintained at a temperature lower than or equal to 10 °C. Then, a solution prepared by dissolving 1.78g of sodium nitrile in 8.7g of water at a temperature of 5 °C, was added. Furthermore, after stirring for 15 minutes, 20g of carbon black having surface area of 320m 2 /g and DBP oil absorption of 120ml/100g is added in the mixed condition. Then, further stirring was performed for 15 minutes. Obtained slurry was filtered by Toyo Roshi No. 2 (made by Advantice Co.). Then, pigment particle was washed sufficiently and dried in an oven at a temperature of 110 °C. Thereafter, by adding water to the pigment, a pigment solution having a pigment concentration of 10 Wt.% was prepared. Therefore, a pigment dispersion liquid, in which self-dispersion type carbon black charged to have anion property and coupled with hydrophilic radical via a phenyl radical on the surface, as expressed by the following chemical formula: As can be clear from respective composition set forth above, depending upon content of acetylenol, the pigment ink and the dye ink of black are set as low penetrative ink and the treatment liquid and respective inks of C, M, Y are set as high penetrative ink, respectively. In the black ink, as anionic carbon black dispersing element, it is preferred to use a self-dispersion type carbon black dispersing element, in which at least one kind of hydrophilic radical is coupled on the surface of the carbon black directly or via another atomic group. As self-dispersion type carbon black, one having ionicity is preferred, and one charged to have anionic property is preferred. When carbon black is charged to have anionic property, the hydrophilic radical to be coupled with the surface of carbon black may be -COOM, -SO 3 M, -PO 3 HM, -PO 3 M 2 , -SO 2 NH 2 , -SO 2 NHCOR and so on (wherein M represents one of hydrogen atom, alkali metal, ammonium and organic ammonium, R represents alkyl radical having carbon atom in a range of 1 to 12, phenyl radical which may have substituent group, or naphthyl radical which may have substituent group), for example. In this embodiment, it is especially preferred to use those charged to have anionic property with coupling -COOM or -SO 3 M on the surface of carbon black. "M" in the hydrophilic radical may be alkali metal such as lithium, sodium, potassium or the like. Alternatively, the hydrophilic radical may be organic ammonium such as mono-, di-, or tri-methyl ammonium, mono to triethyl ammonium, or mono-, di-, or tri-methanol ammonium. As a method for obtaining carbon black charged to have anionic property, such as for linking -COONa on the surface of carbon black, for example, a method for oxidizing carbon black with hydrochlorite soda can be considered. Of course, the present invention is not limited to these. In this embodiment, it is preferred to use carbon black, on the surface of which hydrophilic radical is coupled with other atom group. As other atom group, alkyl group having carbon atom in a range of 1 to 12, phenyl radical which may have substituent group, or naphthyl which may have substituent group may be used. In addition to the foregoing example, -C 2 H 4 COOM, -PhSO 3 M, or -PhCOOM and so on (wherein Ph represents phenyl radical) may be used. However, as a matter of course, the present invention is not limited to those exemplified above. Carbon black, to the surface of which the anionic radical set forth above is bound directly or via other atom group may be prepared by the following method, for example. Namely, as a method for introducing -COONa radical on the surface of carbon black, a method of performing oxidation process for commercially available carbon black with hydrochlorite soda, for example, may be used. On the other hand, for example, as a method for binding -Ar-COONa radical (wherein Ar represents aryl radical) on the surface of carbon black, a method to bind diazonium prepared by acting nitrous acid to NH 2 -Ar-COONa radical on the surface of the carbon black, may be used. However, as a matter of course, the present invention should not be limited to these method. In the self-dispersion type pigment to be contained in the ink of this embodiment it is preferred that 80% or more of the particle thereof have particle size within a range of 0.05 to 0.3 µm, more particularly within a range of 0.1 to 0.25 µm. A method of preparation of such ink is as explained in the foregoing embodiment. Carbon black in the no dispersant pigment ink per se does not require addition of pigment dispersion resin or surface-active agent to attain superior water dispersion ability in comparison with the conventional carbon black. Therefore, in comparison with the conventional pigment ink, carbon black set forth above is advantageous in higher fixing ability, higher wetting ability and so on. Thus, such carbon black is superior in reliability as used in the printing head. By using the mixture ink of black in this embodiment, for a liquid, in which carbon particulate and black dye charged at the same polarity are mixed and dispersed, the treatment liquid containing different polarity of high molecular is reacted. In this embodiment, the ink ejection openings in each printing head are arrayed in a density of 600 dpi. Printing is performed at a dot density of 600 dpi in the feeding direction of the printing paper. Therefore, the dot density of the image or the like to be printed in the embodiment is 600 dpi in both of row direction and column direction. Ejection frequency of respective dot is 4 KHz. Accordingly, a feeding speed of the printing paper becomes about 170 mm/sec. Furthermore, a distance D i between the heads 101Bk1 and 101Bk2 of the mixed ink and the treatment liquid of the head 101S (see Fig. 7) is 80 mm. Accordingly, a period from ejection of the black ink to ejection of the treatment liquid becomes about 0.48 sec. The ejection amount of each printing head is 15 pl per one ejection. Even when an interval from ejection of the black ink Bk to ejection of the treatment liquid S is set at 0.1 seconds, substantially similar result of evaluation could be obtained. Next, for effect and comparison concerning printing quality and so on upon performing printing for a predetermined image of black by this embodiment, explanation will be given using the following tables 2 and 3. In the foregoing table 2, similarly to this embodiment, both comparative examples show the case where the same predetermined image is printed at resolution of 600 dpi. The first comparative example 1 is a system employing only one head ejecting the pigment ink in an amount of 30 pl per one ejection and not using the treatment liquid, and the second comparative example 2 is a system using a head ejecting a dye ink of black in an amount of 30 pl per one ejection and a head ejecting the treatment liquid having relatively low penetration in an amount of 15 pl per one ejection. The embodiment and the comparative examples in the foregoing table 2 perform printing of the predetermined image on mutually different 6 kinds of printing papers and the table 2 shows the results of measurement of OD value and so on. Among evaluation items shown in the table 2, the OD value is measured using a Machbeth density measuring device. A timing, at which water resistance becomes effective, is a timing where disturbance of image is hardly recognized when water is dripped after printing. Also, a fixing ability is a timing where set off is not caused upon discharging of the printed product. As is clear from the table 2, in case where the system shown in this embodiment, the system is particularly superior in OD value and fixing ability. In this embodiment of the apparatus shown in Fig. 7, both of the black inks ejected from the heads 101Bk1 and 101Bk2 for black ink were the pigment inks in the case of the comparative example 3 and the dye inks in the case of the comparative example 4. It can be appreciated that the embodiment exhibits superior OD value. Namely, concerning this OD value, in this embodiment where the treatment liquid is applied for the ink, in which the pigment requiring no dispersant and dye are mixed, it obtains higher OD value than the case where the treatment liquid is applied to only pigment or only dye. When comparison is made in terms of suppression of feathering ("blur" or "soaking out") or restriction of lowering of sharpness (restriction of "overflow"), the embodiment exhibits superior effect than the comparative examples. Even when an interval from ejection of the black ink Bk to ejection of the treatment liquid S in table 3 is set as 0.1 seconds, substantially similar result of evaluation could be obtained. The full-multi type printing apparatus described above is used in a condition where the printing head is fixed during printing operation. Therefore, a period required for feeding the printing paper substantially correspond a period required for printing. Thus, the present embodiment is suitable for high speed printing. Accordingly, by application of the present embodiment to the high speed printing apparatus, high speed printing function can be further improved. Furthermore, in view of the OD value and restriction of "soaking out", "overflow" and so on, high quality printing can be achieved. While the embodiment of the printing apparatus is employed in a printer in the most typical case, the application is not limited to this but can be constructed as a printing portion of copy machine, facsimile and so on. The effect of the embodiment explained with reference to tables 2 and 3 is not limited to the construction employing two heads with respect to black mixed ink but can be a construction employing a single head with ejection amount of 30 pl. (Second Embodiment) Fig. 11 is a general perspective view showing a construction of a serial type printing apparatus 5 according to the second embodiment of the present invention. Namely, the printing apparatus which ejects the treatment liquid after application of the mixed ink on the printing medium for causing reaction, is not limited to the full-line type but can be a serial type apparatus. Similar elements to those illustrated in Fig. 7 will be identified by like reference numerals and detailed description thereof is omitted in order to avoid redundant disclosure. The printing paper 103 as the printing medium is inserted from a paper feeding portion 105 and discharged through a printing portion 126. In the embodiment, generally widely used inexpensive plain paper is used as the printing paper 103. In the printing portion 126, the carriage 107 is constructed to mount the printing heads 101Bk, 101S, 101C, 101M and 101Y and to move reciprocally along the guide rail 109 by a driving force of the not shown motor. The printing head 101Bk ejects the mixed ink of black discussed in the former embodiment. On the other hand, the printing heads 101S, 101C, 101M and 101Y respectively ejects the treatment liquid, cyan ink, magenta ink and yellow ink and are driven in sequential order for ejecting the treatment liquid and inks. To respective heads, the ink and the treatment liquid are supplied from respectively corresponding ink tanks 108Bk, 108S, 108C, 108M and 108Y. Upon ink ejection, drive signals are supplied to electrothermal transducers, namely heaters, provided for respective of the ejection openings of respective heads to thereby apply thermal energy to the ink and the treatment liquid for generating bubble. A pressure upon bubbling is used to perform ejection of the inks and the treatment liquid. For each head, 64 ejection openings are arranged at a density of 360 dpi. These 64 ejection openings are arranged in alignment in the same direction as the feeding direction of the printing paper 103, namely in substantially perpendicular direction to scanning direction of each head. In the embodiment, ejection amount per each ejection opening is set at 23 pl. A distance between each individual head is 1/2 in. Accordingly, the distance between the heads 101Bk and 101S becomes 1/2 inch. Since a printing density in the scanning direction is 720 dpi and ejection frequency of each head is 7.2 KHz, a period from ejection of the pigment ink of the head 101 Bk to ejection of the treatment liquid of the head 101S becomes 0.05 sec. Figs. 12A to 12C are diagrammatic illustration showing ejection opening arrays of other examples of a head construction in the serial printing apparatus shown in Fig. 11. As shown in Fig. 12A, the head may be constructed to have two ejection portions (ejection portions 101Bk1 and 101Bk2) for ejecting black ink as the mixed ink, and the ejection portion 101S ejecting the treatment liquid is arranged therebetween. In this case, after application of the mixed ink of black, the treatment liquid is applied, and subsequently the mixed ink of black is further applied. The head construction shown in Figs. 12B and 12C as well as Fig. 12A, is constructed, in which the head constructions for several inks or treatment liquid are integrated. Of course, in these head unit of integral construction, the ejection openings per the inks or the treatment liquid or liquid chambers and so forth communicated thereto are mutually separated. Accordingly, each ejection portion is similar to the head of each ink or treatment liquid. Similarly to Fig. 12A, Fig. 12B shows an example, in which two ejection openings ejecting black ink of the mixed ink. However, this embodiment, the ejection portions 101Bk1 and 101BK2 for the mixed ink and the ejection portion for the treatment liquid are arranged so that the mixed ink is ejected through two ejection portions 101Bk1 and 101Bk2 in advance of ejection of the treatment liquid. With such construction, after deposition of two droplets of black ink of the mixed ink, the treatment liquid is applied. Fig. 12C shows an example which is similar in arrangement and number to the embodiment shown in Fig. 11 in terms of arrangement and number of ejection portion 101Bk ejecting the mixed ink of the black ink and the ejection portion 101S ejecting the treatment liquid, and is differentiated in constructions of the ejection portions of respective of C, M and Y inks. Respective two ejection portions of respective of C, M, Y inks (ejection portions 101C1, 101C2, ejection openings 101M1, 101M2 and ejection portions 101Y1, 101Y2) are provided. The ejection portions 101C1, 101M1 and 101Y1 and ejection portions 101C2, 101M2 and 101Y2 are respectively arranged in the direction perpendicular to the scanning direction, per each ink. In this head construction, a plurality of times of scanning with feeding of the printing paper between each scan is effected for overlaying respective inks of C, M and Y. Two ejection portions of each ink, respectively eject high density and low density inks. As shown in Figs. 12A and 12B, when two ejection portions of the mixed ink of black ink are present, for example, content of no dispersant pigment and the dye in the mixed ink to be ejected from respective ejection portions are the same in either ejection openings. However, the contents of no dispersant pigment and the dye in the mixed ink to be ejected from respective ejection portions may be differentiated. For example, a ratio of the pigment and the dye may be 3 : 7 in the ejection portion 101Bk1 and 7 : 3 in the ejection portion 101Bk2. Conversely, the ratio may be 7 : 3 in the ejection portion 101Bk1 and 3 : 7 in the ejection portion 101Bk2. (Third Embodiment) In further embodiment of the present invention, as shown in Fig. 12A, the printing head or ejection portion are arranged. Namely, in Fig. 12A, the mixed ink of black is ejected from ejection portions 101Bk1 and 101Bk2, and the treatment liquid is ejected from the ejection portion 101S. Then, the mixed ink, the treatment liquid and the mixed ink are ejected in sequential order. In this embodiment, in each ejection portion, the ejection openings are arranged at a density of 600 dpi. The ejection amount of each ejection opening is 15 p1. An interval between the ejection portions is 1/2 inch similarly to the foregoing second embodiment. The ejection frequency is 10 KHz, and the resolution in printing is 600 dpi in both of the auxiliary scanning direction (paper feeding direction) and primary scanning direction (head scanning direction). Therefore, interval of ejection of the mixed ink and the treatment liquid becomes 30 msec. The treatment liquid contains 0.7% of acetylenol to have high penetrative property. According to the construction of the embodiment, the OD value of printing of black character or the like as high as 1.5 or higher, can be obtained. Also, fluidizing of the reaction product by the treatment liquid is little, "overflow" or feathering can also be prevented successfully. Since high penetrative type treatment liquid is used, relatively high fixing ability can be achieved. (Fourth Embodiment) In the shown embodiment, the construction of the embodiment illustrated in Figs. 7 and 8 is applied for the mode, in which the pigment ink and the dye ink are ejected individually instead of ejecting the mixed ink. In this case, the head 101Bk1 for the black pigment ink, the head 101Bk2 for the black dye ink, the head 101S for the treatment liquid, and heads for color inks (cyan head 101C, magenta head 101M and yellow head 101Y) of the printing head group 101g are arranged as shown along the feeding direction A of the printing paper 103. Then, by ejecting inks of respective colors, and the treatment liquid, through respective printing heads, printing of black characters or color image is possible. In this embodiment, the black pigment ink and the black dye ink to be ejected through the heads 101Bk1 and 101Bk2 respectively, are low penetrative inks having low penetration speed, and the treatment liquid and cyan, magenta and yellow inks to be ejected through the heads 101S, 101C, 101M and 101Y, respectively are high penetrative inks having high penetration speed. Among compositions of the inks to be used in this embodiment, compositions of the inks different from the former embodiment are as follows: [Dye Ink of Black (Bk)] food black 2 4 Wt.% glycerin 7.5 Wt.% diethylene glycol 7.5 Wt.% urea 7.5 Wt.% water remainder [Pigment Ink of Black (Bk)] pigment dispersion liquid 50 Wt.% glycerin 7 Wt.% triethylene glycol 7 Wt.% acetylenol EH (made by Kawaken Fine Chemical) 0.2 Wt.% water remainder A no-dispersant pigment ink is used in this embodiment. In this ink, it is preferred to use a self dispersion type carbon black dispersion element, in which at least one kind of hydrophilic radical is coupled on the surface of the carbon black dispersion element via other atom group, as an anionic carbon black dispersion element. As the self dispersion type carbon black, the carbon black having ionicity, preferably one charged to have anionic property is preferred. By using the pigment and dye inks of black in the embodiment, for a liquid state, in which carbon black particle and black dye charged into the same polarity are mixed and dispersed, the treatment liquid having high molecular weight of different polarity is reacted. In this embodiment, a distance D i (see Fig. 7) between the head 101Bk1 of the pigment ink and the head 101S of the treatment liquid, is 80 mm. Accordingly, a period from ejection of the pigment ink of black to ejection of the treatment liquid is about 0.48 sec. It should be noted that the ejection amount of the printing head is 15 pl per one ejection. Next, effect relating to printing quality or so on upon performing printing for a predetermined image of black by the embodiment and result of comparison will be explained using following tables 4 and 5. As can be clear from the table 4, in the system of the embodiment, OD value and fixing ability are particularly superior. From this table, it can be appreciated that the embodiment is particularly superior in the OD value. Namely, concerning this OD value, when the treatment liquid is applied to the mixture of the pigment ink and the dye ink such as this embodiment, the foregoing effect is caused by mixing to achieve higher OD value than the case where the treatment liquid is applied to only pigment ink or only dye ink. (Fifth Embodiment) Fig. 13 is a general perspective view showing the serial type printing apparatus according to the fifth embodiment of the present invention. It is clear that the printer, in which the treatment liquid is reacted after the dye ink and the pigment ink are mixed on the printing medium, is applicable not only for the foregoing full-line type, but also for the serial type printing apparatus. Similar elements to those illustrated in Fig. 7 will be identified by like reference numerals and detailed description thereof is omitted, in order to avoid redundant disclosure. The printing paper 103 as the printing medium is inserted from the paper feeding portion 105 and discharged through the printing portion 126. In this embodiment, generally widely used inexpensive plain paper is used as the printing paper 103. In the printing portion 126, the carriage 107 is constructed to mount the printing heads 101Bk1, 101Bk2, 101S, 101C, 101M and 101Y and to move reciprocally along the guide rail 109 by a driving force of the not shown motor. The printing head 101Bk1 ejects the pigment ink of black, and the printing head 101Bk2 ejects the dye ink of black. The printing heads 101S, 101C, 101M and 101Y respectively eject the treatment liquid, cyan ink, magenta ink and yellow ink, are driven for ejecting the ink and the treatment liquid in the foregoing order. The pigment ink of black is no dispersant ink also in this embodiment. To respective heads, the inks and the treatment liquid are supplied from the ink tanks 108Bk1, 108Bk2, 108S, 108C, 108M and 108Y. Upon ink ejection, drive signals are supplied to electrothermal transducers, namely heaters, provided for respective of the ejection openings of respective heads to thereby apply thermal energy to the ink and the treatment liquid for generating bubble. A pressure upon bubbling is used to perform ejection of the inks and the treatment liquid. For each head, 64 ejection openings are arranged at a density of 360 dpi. These 64 ejection openings are arranged in alignment in the same direction as the transporting direction Y of the printing paper 103, namely in substantially perpendicular direction to scanning direction of each head. In the embodiment, ejection amount per each ejection opening is set at 23 pl. A distance between each individual head is 1/2. in. Accordingly, the distance between the heads 101Bk1 and 101S becomes 1 inch. Since a printing density in the scanning direction is 720 dpi and ejection frequency of each head is 7.2 KHz, a period from ejection of the pigment ink of the head 101 Bk1 to ejection of the treatment liquid of the head 101S becomes 0.1 sec. (Sixth Embodiment) In a yet further embodiment of the present invention, in the serial type ink-jet printing apparatus shown in Fig. 13, order of arrangement of the printing heads is modified, and associating with this, order of application of the dye ink and pigment ink of black and the treatment liquid is modified. Namely, in Fig. 13, the arrangement of the printing heads 101Bk2 and 101S is modified (other heads are the same as those of the fifth embodiment). Therefore, the pigment ink of black, the treatment liquid, the dye ink of black are ejected on the printing medium in that order. The distance between the heads and ejection frequency of respective head are similar to the second embodiment. According to this embodiment, fluidization of the reaction product of the ink and the treatment liquid can be restricted in comparison with the case where the treatment liquid is applied after application of the pigment ink and the dye ink. Therefore, occurrence of "overflow" and "sweep" can be successfully suppressed. In the shown embodiment, the self dispersion type pigment ink is used for the pigment ink. While the pigment ink of black is ejected from the head 101Bk1 and the dye ink of black is ejected from the head 101Bk2 in the foregoing explanation, it is also possible to eject the dye ink of black from the head 101Bk1, and the pigment ink of black from the head 101Bk2. Even with the latter construction, the equivalent effect to that achieved by the former can be achieved. Even when an interval from ejection of the black ink Bk to ejection of the treatment liquid S is set at 0.1 seconds, substantially similar result of evaluation could be obtained. Here, furthermore, detailed explanation of the phenomenon and prediction concerning the mechanism concerning this case are provided. At first, there is a preferred relationship between a ratio of (self-dispersion type) pigment and dye in the ink (from 100% pigment to 100% dye) and a ratio of cationic high polymer or polyaryl amine (hereinafter referred to as PAA) and cationic surface active agent or Benzelkonium chloride (hereinafter referred to as EBK) in the treatment liquid (from 100% PAA to 100% EBK). Namely, while the treatment liquid is set to contain 4% of PAA and 0.5% of EBK (ratio of PAA is about 90%) in the shown embodiment, by varying the ratio of the pigment and dye in the ink as shown in Fig. 14A to 14C, a result where OD value, striking through property, edge sharpness become maximum, can be obtained in the vicinity of 50%. However, according to increase of ratio of EBK in the treatment liquid, the optical value (peak) of the quality is shifted toward greater ratio of the pigment. Conversely, making the ratio of PAA closer to 100%, the peak is shifted toward greater ratio of the dye. However, the peak of the OD value is not shifted significantly. The foregoing phenomenon may be explained by the following reason (predicated mechanism). As a model, the self-dispersion type pigment is in a form as illustrated in Fig. 15A. Namely, the pigment is in a burr-like form having a large number of fibrous polar group (anionic radical) on the periphery of pigment. PAA as cationic high polymer is a cord-like substance having a plurality of cationic radical in one molecule as shown in Fig. 15D. When self-dispersion type pigment and PAA are mixed, high polymer of PAA may wreathe around the periphery of self-dispersion type pigment as shown in Fig. 16. However, since it is not geometrically possible for all of the cationic radicals of the PAA to be coupled with anionic radicals of the pigment, the coupled substance as a whole is in a condition having cationic property as shown in Fig. 16. Accordingly, reaction product generated by fine particle pigment and PAA has small intermolecular force to cause electrical repelling, making it difficult to aggregate into large blocks. As a result, when dye is not contained, these fine particles may appear as bleeding in smoke form on the periphery of dot. However, when dye (Fig. 15B) and pigment are present in the ink in admixing manner, PAA and dye are coupled to be gel form to serve as a kind of binder for binding between pigments (see Fig. 17). However, when ratio of pigment versus dye becomes large, a part of the fine pigment tends to be in smoke form to degrade sharpness of the edge. Here, when EBK as cationic surface active agent is contained in the ink in addition to PAA, the EBK (Fig. 15C) may serve to aggregate fine pigment particles, and in conjunction therewith to perform buffering function in reaction of dye and PAA promoting gelation to capture fine particle (see Fig. 18). In Figs. 16 to 18, reaction mode at a boundary portion between two pigments is preliminary shown. However, reaction mode at another portion is not shown because it is complicated. Thus, when PAA is bound with dye, bound substance becomes stable in energy. When EBK is bound with self-dispersion type pigment, stability in energy is also established. Namely, mode of reaction may have a kind of selectivity. Therefore, when the ratio of EBK in the treatment liquid becomes large, the optimal value of the quality is shifted toward greater ratio of pigment. Conversely, when the ratio of PAA becomes large, the optimal value of the quality is shifted toward greater ratio of dye. Here, when the ratio of PAA is high, in order to improve possibility of avoiding strike through and causing edge sharpness, the dye may be increased to restrict flow ability of fine pigment particle. However, the reaction product generated by reaction of PAA and only dye, is small in size. Therefore, when penetration ability of the treatment liquid is increased for improving fixing ability, dye may penetrate into the paper in depth direction to make it impossible to obtain high OD value. Therefore, pigment is required. It should be appreciated that presence of the self-dispersion type pigment and dye as coloring material in the ink and presence of high molecular insolubilizing agent in the treatment liquid for making the coloring material in the ink insoluble or for breaking its dispersion are preferred, even if penetration ability of the treatment liquid is not increased. The present invention has been described in detail with respect to the preferred embodiments, and it will now be apparent from the foregoing to those skilled in the art that changes and modifications may be made.

Claims: An ink jet recording apparatus comprising: first ink ejection means (101BK, 101Bk1) and a supply of ink for the first ink ejection means, the first ink ejection means being arranged to eject a first ink which comprises a self-dispersion type pigment and a dye as colouring materials, the apparatus further comprising treatment liquid ejection means (101S) and a supply of treatment liquid, effective to render insoluble the said dye in the first ink and to cause breakage of the dispersion of the said pigment in the first ink, the treatment liquid ejection means being arranged to eject the treatment liquid, the apparatus being arranged so that, in use, the first ink and the treatment liquid mix on the recording medium onto which they are ejected. Apparatus according to claim 1 which is arranged to eject a drop of the first ink from the first ink ejection means before ejecting a drop of the treatment liquid from the treatment liquid ejection means to mix with it. Apparatus according to claim 2 comprising second ink ejection means (101Bk2) and a supply of ink for the second ink ejection means, the second ink ejection means being arranged to eject an ink which comprises at least one of a self-dispersion type pigment and a dye as colouring material, the apparatus being arranged to eject a drop of ink from the second ink ejection means, to mix with the drop of the first ink and the drop of the treatment liquid, after the drop of the first ink has been ejected from the first ink ejection means. Apparatus according to claim 3 which is arranged to eject the drop of the ink from the second ink ejection means before ejecting the drop of the treatment liquid. Apparatus according to claim 3 which is arranged to eject the drop of ink from the second ink ejection means after ejecting the drop of the treatment liquid. Apparatus according to any one of the preceding claims in which the first ink has a Ka value of less than 1.0 ml/(m 2 ·ms 1/2 ) by the Bristow method. Apparatus according to any one of the preceding claims in which the first ink is black ink. An ink jet recording apparatus comprising a supply of a pigment ink primarily containing self-dispersion type pigment as the colouring material, a supply of dye ink primarily containing dye as the colouring material, and a supply of treatment liquid effective to render insoluble the said dye in the dye ink and to cause breakage of the dispersion of the pigment in the pigment ink, pigment ink ejection means (101Bk1), dye ink ejection means (101Bk2) and treatment liquid ejection means (101S), the apparatus being arranged so that, in use, the pigment ink and the dye ink each mix with the treatment liquid, and mix with each other at least partially, on the recording medium onto which they are ejected. Apparatus according to claim 8 which is arranged to eject a drop of the dye ink before ejecting a drop of the pigment ink to mix with it. Apparatus according to claim 8 which is arranged to eject a drop of the pigment ink before ejecting a drop of the dye ink to mix with it. Apparatus according to any one of claims 8 to 10 which is arranged to eject a drop of treatment liquid after ejecting both a drop of dye ink and a drop of pigment ink to mix with it. Apparatus according to any one of claims 8 to 10 which is arranged to eject a drop of treatment liquid before ejecting one and after ejecting the other of a drop of dye ink and a drop of pigment ink to mix with it. Apparatus according to any one of claims 8 to 12 in which the pigment ink and the dye ink both have a Ka value of less than 1.0 ml/(m 2 ·ms 1/2 ) by the Bristow method. Apparatus according to any one of claims 8 to 13 in which the pigment ink and the dye ink are black inks. Apparatus according to claim 7 or claim 14 comprising a cyan ink ejection means (101C) and a supply of cyan ink therefor, a magenta ink ejection means (101M) and a supply of magenta ink therefor, and a yellow ink ejection means (101Y) and a supply of yellow ink therefor. Apparatus according to any one of the preceding claims in which said self-dispersion type pigment has at least one kind of anionic radical coupled on the surface thereof directly or through an another atomic group. Apparatus according to claim 16 in which said anionic radical is selected from the group of anionic radicals consisting of -COOM, -SO 3 M, -PO 3 HM, -PO 3 M 2 , -SO 2 NH 2 , -SO 2 NHCOR in which M represents one of hydrogen, alkali metal, ammonium and organic ammonium, and R represents alkyl radical having 1 to 12 carbon atoms, phenyl radical which may have a substituent group, or naphthyl radical which may have a substituent group. Apparatus according to claim 16 or claim 17 in which said other atomic group is alkyl radical having 1 to 12 carbon atoms, phenyl radical which may have substituent group, or naphthyl radical which may have substituent group. Apparatus according to any one of claims 16 to 18 in which at least 80% of particles of said pigment have a grain diameter of 0.05 to 0.3 µm. Apparatus according to any one of claims 16 to 18 in which at least 80% of particles of said pigment have a grain diameter of 0.1 to 0.25 µm. Apparatus according to any one of the preceding claims in which the treatment liquid has a Ka value of greater than or equal to 5.0 ml/(m 2 ·ms 1/2 ) by the Bristow method. Apparatus according to any one of the preceding claims in which the said ejection means are arranged in a predetermined positional relationship, the apparatus comprising control means (201,210) for causing relative movement between the ejection means and the recording medium and for controlling ejection of ink and treatment liquid by the ejection means. Apparatus according to claim 22 in which the said ejection means are arranged in a sequential order in a predetermined direction, and the control means is arranged to control ejection by the ejection means so as to cause ejection of drops, to be mixed with each other on the recording medium, from the ejection means in said sequential order. Apparatus according to any one of the preceding claims which is capable of recording onto a recording medium over a predetermined recording width of the recording medium, and in which the said ink ejection means and treatment liquid ejection means each have an array of ejection openings extending across the entirety of the said recording width. Apparatus according to claim 22 or claim 23 comprising drive means for driving the said ink ejection means and treatment ejection means relative to the recording medium while maintaining their predetermined positional relationship, and in which the control means is arranged to control the drive means so as to scan the ejection means across the recording medium. A printing method comprising ejecting a first ink and a treatment liquid onto a recording medium so that they mix on the recording medium, the first ink comprising a self-dispersion type pigment and a dye as colouring materials, and the treatment liquid being effective to render insoluble the said dye in the first ink and to cause breakage of the dispersion of the said pigment in the first ink. A method according to claim 26 comprising ejecting a drop of the first ink before ejecting a drop of the treatment liquid to mix with it. A method according to claim 27 comprising ejecting a second drop of ink to mix with the said drop of the first ink and the said drop of the treatment liquid, the second drop of ink being ejected after the said drop of the first ink, and the ink of the second drop comprising at least one of a self-dispersion type pigment and a dye as colouring material. A method according to claim 28 comprising ejecting the said second drop of ink before ejecting the said drop of treatment liquid. A method according to claim 28 comprising ejecting. the said second drop of ink after ejecting the said drop of treatment liquid. A method according to any one of claims 26 to 30 in which the first ink has a Ka value of less than 1.0 ml/(m 2 ·ms 1/2 ) by the Bristow method. A method according to any one of claims 26 to 31 in which the first ink is black ink. A printing method comprising ejecting a pigment ink, a dye ink and a treatment liquid onto a recording medium so that the inks each mix with the treatment liquid, and mix with each other at least partially, on the recording medium, the pigment ink primarily containing a self-dispersion type pigment as the colouring material, the dye ink primarily containing dye as the colouring material, and the treatment liquid being effective to render insoluble the said dye in the dye ink and to cause breakage of the dispersion of the said pigment in the pigment ink. A method according to claim 33 which comprises ejecting a drop of the dye ink before ejecting a drop of the pigment ink to mix with it. A method according to claim 33 which comprises ejecting a drop of the pigment ink before ejecting a drop of the dye ink to mix with it. A method according to any one of claims 33 to 35 which comprises ejecting a drop of treatment liquid after ejecting both a drop of dye ink and a drop of pigment ink to mix with it. A method according to any one of claims 33 to 35 which comprises ejecting a drop of treatment liquid before ejecting one and after ejecting the other of a drop of dye ink and a drop of pigment ink to mix with it. A method according to any one of claims 33 to 37 in which the pigment ink and the dye ink both have a Ka value of less than 1.0 ml/(m 2 ·ms 1/2 ) by the Bristow method. A method according to any one of claims 33 to 38 in which the pigment ink and the dye ink are black inks. A method according to any one of claims 26 to 39 in which said self dispersion type pigment has at least one kind of anionic radical coupled on the surface thereof directly or through another atomic group. A method according to claim 40 in which said anionic radical is selected from the group of anionic radicals consisting of -COOM, -SO 3 M, -PO 3 HM, -PO 3 M 2 , -SO 2 NH 2 , -SO 2 NHCOR in which M represents one of hydrogen, alkali metal, ammonium and organic ammonium, and R represents alkyl radical having 1 to 12 carbon atoms, phenyl radical which may have a substituent group, or naphthyl radical which may have a substituent group. A method according to claim 40 or claim 41 in which said other atomic group is alkyl radical having 1 to 12 carbon atoms, phenyl radical which may have a substituent group, or naphthyl radical which may have a substituent group. A method according to any one of claims 40 to 42 in which more than or equal to 80% of particles of said pigment have a grain diameter of 0.05 to 0.3 µm. A method according to any one of claims 40 to 42 in which more than or equal to 80% of particles of said pigment have a grain diameter of 0.1 to 0.25 µm. A method according to any one of claims 26 to 44 in which the treatment liquid has a Ka value of greater than or equal to 5.0 ml/(m 2 ·ms 1/2 ) by the Bristow method.

Inventors: KOITABASHI NORIBUMI, KOITABASHI, NORIBUMI
Applicants: CANON KK, CANON KABUSHIKI KAISHA
Application year: 1998
Main classification: B41J2
IPC codes: B41J2, B41M5