CN1782001A

CN1782001A - Ink composition, printing method using the same and printed image obtained using the same, and ink set and ink head

Info

Publication number: CN1782001A
Application number: CNA2005101314191A
Authority: CN
Inventors: 加本贵则; 森本清文; 上原诚; 中津裕美; 木元正纪
Original assignee: Sharp Corp
Current assignee: Sharp Corp
Priority date: 2002-09-18
Filing date: 2003-09-18
Publication date: 2006-06-07
Anticipated expiration: 2023-09-18
Also published as: JP2004107480A; CN1782001B; JP4272399B2

Abstract

An ink composition is prepared in such a manner that a difference between a dynamic surface tension (mN/m) measured by a maximum bubble pressure method at a temperature of 24 to 26 DEG C. and a static surface tension (mN/m) is within a range from 0 to 7 (mN/m). The ink composition is stored in an ink tank of an ink head, and is supplied from the ink tank to an ink chamber having a discharge port, and a voltage is applied to partitions formed by a piezoelectric material to apply a pressure by the partitions to the ink composition stored in the ink chamber, whereby a liquid droplet of the ink composition is discharged from the discharge port and the liquid droplet is deposited on a recording material to record an image.

Description

Ink composite, the writing-method of using it and document image, printing ink group and ink gun

The application is to be that September 18, application number in 2003 are 03165009.0, exercise question is divided an application for " ink composite, the writing-method of using it and document image, printing ink group and ink gun " the applying date.

Technical field

The present invention relates to ink composite suitable in ink jet recording method, adopt the recording method and the document image of this ink composite, and printing ink group (ink set) and ink gun (ink head).

Background technology

Ink jet recording method is a kind of by kinetic energy or heat energy, ink composite (following also be called simply " printing ink ") drop is discharged and flies out, and make such drop attached to the method as document image on the recording materials such as paper.

Before this, the ink characteristics that in ink-jet recording method (below be also referred to as " ink for inking "), uses, the physical properties of usable surface tension force or viscosity and so on is represented.People once attempted to regulate the drying property of printing ink or improve the picture quality that forms by limiting these physical propertiess.

For example, the someone proposes a kind of like this ink jet recording method, and it is by comprising that surface tension is as the Weber number of parameter with comprise the product limit droplet of ink of viscosity as the Reynolds number of parameter.Allow the product of Weber number and Reynolds number keep within the specific limits, can realize high-quality image (referring to the bulletin JP-B2 2968010 of Japan's unexamined patent).A kind of ink jet recording method (referring to the bulletin JP-B2 63-65034 (1988) of Japan's unexamined patent) that uses surface tension specified range printing ink is also proposed.

The surface tension of using in JP-B2 2968010 and the described technology of JP-B2 63-65034 all is the surface tension of fluid surface when reaching equilibrium state, i.e. static surface tension.Usually also be static surface tension (people such as Akio Kinoshita for example as the surface tension of ink for inking specific performance index, " Tokushu Kinou Inki no Jissai Gijutu (printing ink practical technique) " with specific function, popular edition the 1st edition, CMC Co., on November 15th, 1999, the 6th～7 page).In such a manner, most characteristics of representing jetted ink with the static surface tension in the surface tension.

But, only also be difficult to fully represent the characteristic of printing ink with static surface tension.

In the ink jet recording device with the ink jet recording method document image, printing ink is full of the print cartridge of ink gun, and ink droplet is discharged from print cartridge front end relief outlet in a continuous manner, on recording materials, thus document image.When printing ink is discharged continuously, when discharging with ink droplet, form the fresh surface of printing ink at relief outlet, it is new meniscus, and, for example when relief outlet begins to form new generation surface, before being about to discharge, moment of discharging moment, when flying out, dropping on recording materials in ink droplet, ink droplet is permeated in recording materials such as paper etc., the surface tension difference of printing ink.For example, relief outlet begins to form fresh surface or ink droplet and infiltrates in the recording materials process such as paper, the surface tension of so slow mobile status, and when discharging between the surface tension of quick travel state, all changing constantly.Here, slowly mobile status can be regarded as stationary state, and think surface tension constantly all from stationary state to dynamic change.Therefore, in order fully to represent the characteristic of ink for inking, be necessary to consider dynamic surface tension, it is that fluid surface reaches the surface tension in the equilibrium state process.

The importance of dynamic surface tension was all described in various reference.For example, Schwartz, J. aqueous coating static surface tension and dynamic surface tension are estimated, point out that dynamic surface tension is the important factor that aqueous coating forms coated membrane, low dynamic surface tension can effectively form evenly good coated membrane (referring to " importance of low dynamic surface tension in aqueous coating ").

Medina, S.W. and Sutovich, M.N. the importance of dynamic surface tension in flying print is discussed, surface tension when proposing static surface tension and be fluid surface and reaching equilibrium state, be an index of performance (penetrating paper etc. as ink droplet) when effectively representing the slow mobile status of printing ink, but be not an index of performance when effectively representing printing ink quick travel state when flying print (for example).On the other hand, they propose dynamic surface tension is that the tensio-active agent that expression contains in the printing ink produces new ink pellet surface continuously to relief outlet, perhaps to the index of the transfer ability that is attached to ink droplet on the recording materials and the interface between the recording materials continuously.Promptly, tensio-active agent is because of newly forming on the surface at printing ink, or on the interface between ink droplet and the recording materials, be adsorbed and reduce its surface tension, therefore, to printing ink newly form the surface or between ink droplet and recording materials the transfer ability at interface high more, ink surface tension reduction effect is just high more during the quick travel state, thereby the printing ink dynamic surface tension reduces (referring to " tensio-active agent is used to prepare VOC Comoliant water-based inks ").

Also proposed a kind of ink composite and a kind of recording method that utilizes this ink composite that is suitable for ink jet recording method, a kind of definite relation has been arranged between the dynamic surface tension of said composition and the viscosity.This technology shows, satisfy at ink composite [life-span 0 millisecond time dynamic surface tension (dyne/cm)]+scope of [viscosity (cP)]=42～49 conditions in, can obtain gratifying print characteristic (referring to the bulletin JP-B2 2516218 of Japan's unexamined patent).

But, in the technology of No. 2516218 records of JP-B2, add the condition equation of viscosity number with dynamic surface tension, determined dynamic surface tension, but because the unit of dynamic surface tension and viscosity number is different, i.e. the dimension difference, so such condition equation value is skimble-skamble.

This technology shows that also tensio-active agent does not help the reduction of dynamic surface tension.But the known surface promoting agent obviously helps wettability or printing ink the performance on recording materials of ink for inking on the print cartridge inwall usually, and it is not only the main component of printing ink, and is the important factor of control dynamic surface tension.For example, Schwartz, J. in aforementioned " importance of low dynamic surface tension in the aqueous coating " literary composition, change static surface tension and dynamic surface tension with some tensio-active agent, evaluated them to being coated with film formed influence, pointed out that the reduction of dynamic surface tension can effectively reduce the generation of the contraction of coated film, the hole of filming and the bubble of wherein holding back.

In addition, this technology has only been determined dynamic surface tension, but does not determine static surface tension.As mentioned above, in ink jet recording method, the surface tension of printing ink all from dynamically changing to static state, therefore, needs fully to represent the dynamic surface tension and the static surface tension of ink for inking constantly.

In addition, this technology has only been determined the dynamic surface tension of quick travel state, particularly 0 millisecond dynamic surface tension, but does not determine the dynamic surface tension of slow mobile status.As mentioned above, in ink jet recording method, change between the surface tension of the slow mobile status of being everlasting during the surface tension of printing ink and the surface tension of quick travel state, so the dynamic surface tension of the dynamic surface tension of quick travel state and slow mobile status all is important for the characteristic of abundant demonstration ink for inking.

Summary of the invention

An object of the present invention is by determining the relation between dynamic surface tension and the static surface tension, a kind of good composition stability and that the high quality document image is provided of discharging that has is provided when being used for ink jet recording method, use the recording method and the document image of this ink composite, and printing ink group (ink set) and ink gun (ink head).

Another object of the present invention is by the relation between the dynamic surface tension of the dynamic surface tension of determining the quick travel state and slow mobile status, a kind of good ink composite stability and that the high quality document image is provided of discharging that has is provided when using in ink jet recording method, adopt the recording method and the document image of said composition, and printing ink group and ink gun.

The invention provides a kind of ink composite, it contains a kind of tinting material and medium at least, it adopts the dynamic surface tension of maximum bubble method (maximum bubble pressure method) mensuration down and at 24～26 ℃ of static surface tensions of measuring down of temperature, satisfies the relation of following formula (1) 24～26 ℃ of temperature:

0≤[dynamic surface tension (mN/m)]-[static surface tension (mN/m)]≤7 (mN/m)

(1)

According to the present invention, the dynamic surface tensions of ink composite design mensuration under temperature range is 24～26 ℃ and the difference of static surface tension are kept within the specific limits.In the ink-jet recording device that adopts this ink jet recording method document image, when the ink composite drop is discharged continuously, the relief outlet that the print cartridge front end is provided with in ink gun, produce new ink composite surface continuously, it is fast that thereby ink composite moves, and dynamic surface tension has bigger influence.On the other hand, in print cartridge (inkchamber), after ink composite is discharged, can from ink tank, replenish the ink composite that reduces by capillary action, its additional volume is corresponding to the volume that reduces because of discharge, therefore ink composite moves slowly, can regard static as, thereby static surface tension has very big influence.That is, because dynamic surface tension and static surface tension all exert one's influence when discharging, so the essential balance of considering dynamic surface tension and static surface tension is so that the stable discharge of realization ink composite drop.In addition, by the ink composite drop attached to recording materials on and during document image, this ink composite also shows, quick travel when drop drops on the recording materials, but slack-off gradually afterwards, and when recording materials were absorbent material, ink composite was penetrated in the recording materials.That is, surface tension can be from dynamically becoming static state, and if the difference of dynamic surface tension and static surface tension bigger, the ink composite drying on recording materials needs long time, thereby produces stain (blotting).Therefore, as mentioned above, the difference of dynamic surface tension and static surface tension is kept within the specific limits, if use ink jet recording method, can obtain a kind of ink composite, said composition demonstrates fine and discharges stability and suppress the generation trace on recording materials, and the high quality record image is provided.

In addition, in the present invention, the bubble frequency of mensuration dynamic surface tension is 0.5～35Hz preferably.

According to the present invention, ink composite is designed to the dynamic surface tension of bubble frequency 0.5～35Hz mensuration and the difference of static surface tension is within the specific limits.Whereby, can obtain a kind of ink composite, when using said composition in ink jet recording method, it shows that stable also can being suppressed at of good discharge produces trace on the recording materials, thereby can obtain the high quality record image.

In addition, in the present invention, preferred static surface tension is 20～50mN/m.

According to the present invention, static surface tension is 20～50mN/m.Static surface tension can cause too high perviousness less than 20mN/m, thus ink composite transverse dispersion on the absorptivity recording materials, and the image outline of formation seems unclear.In addition, static surface tension surpasses 50mN/m also can reduce perviousness on recording materials, thereby reduces drying property.In addition, the wettability that this ink composite also is presented on the print cartridge inwall reduces, and hinder toward the supply of ink composite to print cartridge, thereby ink composite can not be full of print cartridge reposefully, can not stably discharge with droplet-like.Therefore, as mentioned above, static surface tension is remained on 20～50mN/m, and the dynamic surface tension of mensuration and the difference of static surface tension are kept within the specific limits, can obtain a kind of ink composite, if when ink jet recording method uses said composition, it has shown good discharge stability, and can be suppressed at and produce trace on the recording materials, thereby obtain the high quality record image.

In addition, in the present invention, comprise in the ink composite that preferably water is as medium.

According to the present invention, the water owing to containing in the ink composite as medium might be suppressed at and produce trace on the recording materials, improves drying property.

In addition, in the present invention, preferably ink composite also comprises tensio-active agent.

According to the present invention, because ink composite also contains tensio-active agent, so, control dynamic surface tension and static surface tension at an easy rate.

In addition, in the present invention, preferred medium is to comprise gylcol ether (glycol ether) and/or polyalcohols.

According to the present invention, because medium contains gylcol ether and/or the polyalcohols that comprises low-steam pressure, so, can obtain wetting effect, discharge stability thereby improve.

In addition, in the present invention, preferred tinting material comprises dyestuff.

According to the present invention, because tinting material comprises dyestuff, so, can suppress relief outlet and stop up, discharge stability thereby improve.

In addition, in the present invention, preferred tinting material comprises pigment.

According to the present invention, because tinting material comprises pigment, so, the document image that might obtain having good photostabilization and water resisting property.

In addition, in the present invention, preferred tinting material comprises the pigment with hydrophilic radical.

According to the present invention, because tinting material comprises the pigment with hydrophilic radical, so, the document image that can obtain having good photostabilization and water resisting property.Also have, because pigment has hydrophilic radical, so, in aqueous ink compositions, can be the stable dispersion state and exist.Therefore, can suppress to produce latch up phenomenon, can obtain the ink composite that a kind of energy acquisition has the document image of high-quality photostabilization and water resisting property, also can not reduce and discharge stability.

In addition, in the present invention, preferred surfactants comprises nonionogenic tenside.

According to the present invention, because tensio-active agent comprises the nonionogenic tenside of the ionogen influence that is difficult for being subjected to coexisting, so the difference of dynamic surface tension and static surface tension can keep within the specific limits, and no matter whether added ionogen in the ink composite.

In addition, in the present invention, preferably contain the above tensio-active agent of micelle-forming concentration.

According to the present invention, described surfactant concentrations is micelle-forming concentration or is higher than micelle-forming concentration.The surface tension that contains the solution of tensio-active agent is increased to micelle-forming concentration along with tensio-active agent and reduces, but in micelle-forming concentration or be higher than micelle-forming concentration and then remain unchanged basically.Therefore, as mentioned above, owing to have micelle-forming concentration or be higher than the tensio-active agent of micelle-forming concentration, might make full use of the effect of tensio-active agent, and remain unchanged basically, thereby the ink composite that can obtain having even character by tensio-active agent control dynamic surface tension and static surface tension value.

In addition, in the present invention, preferably, pigment comprises the C.I. pigment Blue 15: 3 and the C.I. pigment Blue 15: at least a in 4.

According to the present invention, because described pigment comprises the C.I. pigment Blue 15: 3 and the C.I. pigment Blue 15: at least a in 4, so, can obtain a kind of ink composite that can access the good document image of cyan (cyan) color emissivity.

In addition, in the present invention, preferably, pigment comprises the pigment of at least a C.I. of being selected from pigment red 122, C.I. Pigment red 209 and C.I. pigment violet 19.

According to the present invention, because pigment comprises the pigment of at least a C.I. of being selected from pigment red 122, C.I. Pigment red 209 and C.I. pigment violet 19, so, can obtain a kind of ink composite that can generate the red document image of high-quality product.

In addition, in the present invention, preferably, pigment comprises the pigment of at least a C.I. of being selected from Pigment Yellow 73 74, C.I pigment yellow 13 8, C.I Pigment Yellow 73 150 and C.I. Pigment Yellow 73 180.

According to the present invention, because pigment comprises the pigment of at least a C.I. of being selected from Pigment Yellow 73 74, C.I. pigment yellow 13 8, C.I. Pigment Yellow 73 150 and C.I. Pigment Yellow 73 180, so, can obtain a kind of ink composite that can generate the yellow document image of high-quality.

The present invention also provides a kind of recording method, and this method is by the recording method of ink composite attached to document image on the recording materials, and wherein said ink composite is to adopt in the ink composite of the invention described above any.

According to the present invention, by making in the recording method of ink composite attached to document image on the recording materials, utilized the ink composite of any the invention described above, thereby stable high quality document image can be provided.

The present invention also provides a kind of recording method that is used for document image, this method comprises: to the ink composite pressurization, the ink composite drop is discharged, make drop attached on the recording materials, wherein, ink composite is any ink composite that adopts the invention described above.

According to the present invention, owing to be to pressurize to ink composite, the ink composite drop is discharged, drop is attached to the recording method of document image on the recording materials, promptly, in ink jet recording method, adopt the ink composite of any the invention described above, discharge and provide stable high quality document image thereby can stablize.

In addition, in the present invention, described ink composite adopts at least a following ink composite: wherein pigment comprises the C.I. pigment Blue 15: 3 and the C.I. pigment Blue 15: at least a ink composite in 4; Wherein pigment comprise the ink composite that is selected from least a pigment in C.I. pigment red 122, C.I. Pigment red 209 and the C.I. pigment violet 19 and wherein pigment comprise the ink composite that is selected from least a pigment in C.I. Pigment Yellow 73 74, C.I pigment yellow 13 8, C.I. Pigment Yellow 73 150 and the C.I. Pigment Yellow 73 180.

According to the present invention, because ink composite has used at least a ink composite that can obtain the good document image of cyan color emissivity, a kind of ink composite and a kind of ink composite that can obtain the good document image of yellow color emissivity that can obtain the good document image of magenta color emissivity, so, by with above-mentioned three kinds of ink composites stack, can realize the document image of high-density black.

The present invention also provides a kind of document image that adopts above-mentioned recording method record.

According to the present invention,, can obtain the high quality record image owing to adopt this recording method that image is carried out record.

The present invention also provides a kind of printing ink group (ink set), and it comprises:

A kind of ink composite, wherein pigment comprises the C.I pigment Blue 15: 3 and the C.I. pigment Blue 15: at least a pigment in 4;

A kind of ink composite, wherein pigment comprises the pigment of at least a C.I. of being selected from pigment red 122, C.I. Pigment red 209 and C.I. pigment violet 19; With

A kind of ink composite, wherein pigment comprises the pigment of at least a C.I. of being selected from Pigment Yellow 73 74, C.I. pigment yellow 13 8, C.I. Pigment Yellow 73 150 and C.I. Pigment Yellow 73 180.

According to the present invention, because the printing ink group comprises a kind of ink composite that can obtain the good document image of cyan color emissivity; The ink composite of the document image that the ink composite of the document image that a kind of magenta color emissivity is good and a kind of yellow color emissivity are good, so, by with above-mentioned three kinds of ink composites stack, can realize highdensity black recording image.

The present invention also provides a kind of ink gun (ink head), comprising:

Store the ink tank (ink tank) of above-mentioned any ink composite of the present invention;

Print cartridge (ink chamber) has a relief outlet and the ink composite that receives from ink tank that is used to discharge the ink composite drop;

With applying the piezoelectric element that voltage produces deformation, it is provided at least a portion print cartridge, thereby ink composite contained in the print cartridge is exerted pressure; With

Apply the electrode of voltage to piezoelectric element.

According to the present invention, ink gun stores any ink composite of the present invention by ink tank; Hold the ink composite that ink tank provides with print cartridge, this print cartridge has the relief outlet of discharging the ink composite drop; Apply voltage with electrode to piezoelectric element; Produce the strained piezoelectric element ink composite contained in the print cartridge is exerted pressure with using with applying voltage, this piezoelectric element is provided at least a portion print cartridge.Therefore, can obtain a kind of piezoelectric ink-jet head, this ink gun can be tackled the voltage that piezoelectric element applies mutually, discharges the ink composite drop from relief outlet.Also have, because ink tank has stored any ink composite of the present invention, therefore, the ink composite drop can stably be discharged from relief outlet.As the ink gun adopting, the piezoelectric ink jet recording unit that can realize having high reliability.

The present invention also provides a kind of ink gun, comprising:

Store the ink tank of any ink composite of the invention described above;

Print cartridge, it has the relief outlet of discharging the ink composite drop, and receives the ink composite from ink tank;

Be provided in the Heating element (heat generating member) at least a portion print cartridge, this element is suitable for heating the ink composite in the print cartridge, produces bubble therein, thereby exerts pressure to ink composite; With

For apply the electrode that voltage is equipped with to Heating element.

According to the present invention, ink gun stores any ink composite of the present invention by ink tank; Print cartridge is equipped with the ink composite that comes from ink tank, and print cartridge has the relief outlet of discharging the ink composite drop; Apply voltage with electrode to Heating element; And use ink composite in the Heating element heating print cartridge be provided at least a portion print cartridge, produce bubble, thereby exert pressure to ink composite.Therefore, can obtain a kind of hot ink jet type ink gun, it can respond the voltage that Heating element is applied, and discharges the ink composite drop from relief outlet.Also have, because ink tank has stored any ink composite of the present invention, the ink composite drop can stably be discharged from relief outlet.Such ink gun can realize having the hot ink jet type ink-jet recording device of high reliability.

The present invention also provides a kind of ink composite drop to discharge by piezoelectric ink-jet head, attached to the document image of the enterprising line item of recording materials.

According to the present invention, because document image is that the ink composite drop is discharged by piezoelectric ink-jet head, attached to what form on the recording materials, this ink gun can stably be discharged the ink composite drop as mentioned above, therefore, can stably obtain the high quality record image.

The present invention also provides a kind of ink composite drop to discharge by hot ink jet type ink gun, attached to the document image of the enterprising line item of recording materials.

According to the present invention, because document image is that the ink composite drop is discharged through hot ink jet type ink gun, form attached to recording materials, this ink gun can stably be discharged the ink composite drop as mentioned above, so can stably obtain the high quality record image.

The invention provides a kind of ink composite, it contains a kind of tinting material and medium at least, wherein:

Adopt in the dynamic surface tension of maximum bubble method mensuration the dynamic surface tension (σ when bubble frequency is 10Hz down 24～26 ℃ of temperature ₁₀) with the dynamic surface tension (σ of bubble frequency when being 1Hz ₁) difference d (=σ ₁₀-σ ₁) satisfy following formula (2):

0mN/m≤d≤7mN/m (2)

According to the present invention, in the dynamic surface tension that ink composite is designed to measure with maximum bubble method under 24～26 ℃ of temperature, the dynamic surface tension (σ when bubble frequency is 10Hz ₁₀) and the dynamic surface tension (σ of bubble frequency when being 1Hz ₁) difference d (=σ ₁₀-σ ₁) within the specific limits.In ink-jet recording device with the ink jet recording method document image, when the ink composite drop is discharged continuously, print cartridge front end relief outlet in ink gun produces the new surface of ink composite continuously, thereby ink composite quick travel, and the high frequency dynamic surface tension to about 10Hz has big influence, and this dynamic surface tension is corresponding to the dynamic surface tension of quick travel state.On the other hand, in print cartridge, discharge after the ink composite, by capillary action makeup oil ink composition from ink tank, its volume is corresponding to discharging the amount that is reduced, therefore ink composite slowly moves, and the low frequency dynamic surface tension of about 1Hz is had big influence, and this dynamic surface tension is corresponding to the dynamic surface tension of slow mobile status.Promptly, when discharging, because the influence of high-frequency dynamic surface tension and low-frequency dynamic surface tension, so, in order to realize the stable discharge of ink composite drop, must consider the balance of high-frequency dynamic surface tension and low-frequency dynamic surface tension.Also have, drop attached to recording materials on and during document image, this ink composite has shown that drop drops on the recording materials quick travel of moment, but slack-off gradually afterwards, when recording materials were the absorptivity recording materials, ink composite slowly was penetrated in the recording materials.Promptly, the dynamic surface tension of ink composite, become the dynamic surface tension of slow mobile status from the dynamic surface tension of quick travel state, and when the difference of high-frequency dynamic surface tension and low-frequency dynamic surface tension is big, ink composite on the recording materials is dry to need the long time, thereby produces trace.Excessive penetration also can cause back side ink bleed (rearpenetration).Therefore, as mentioned above, be the dynamic surface tension (σ of 10Hz with bubble frequency ₁₀) with bubble frequency be the dynamic surface tension (σ of 1Hz ₁) difference d (=σ ₁₀-σ ₁) design in above-mentioned certain limit, whereby, when in ink-jet recording method, using ink composite, may obtain to discharge excellent in stability, and can suppress the trace on the recording materials, thereby the high quality record image is provided.

In addition, in the present invention, preferably, the dynamic surface tension (σ when bubble frequency is 10Hz ₁₀) with the dynamic surface tension (σ of bubble frequency when being 1Hz ₁) in 20～70mN/m scope.

According to the present invention, the dynamic surface tension (σ when bubble frequency is 10Hz ₁₀) and the dynamic surface tension (σ of bubble frequency when being 1Hz ₁) in 20～70mN/m scope.Work as σ ₁₀And σ ₁During less than 20mN/m, the perviousness of absorptivity recording materials is become too high, thereby the ink composite that is attached on the absorptivity recording materials is diffused into the peripheral region from drop point, thereby the image outline that forms is unintelligible.Work as σ ₁₀And σ ₁When surpassing 70mN/m, the seepage force of absorptivity recording materials became low, thereby the drying property on the absorptivity recording materials reduces.This ink composite has also shown the wettability variation with the print cartridge inwall, hindered the supply of ink composite to print cartridge, thereby ink composite is difficult to filling ink cartridges reposefully, and, can not discharge so that droplet-like is stable.In addition, be difficult to form the new generation surface of ink composite at the relief outlet of print cartridge front end, promptly be difficult to control meniscus with intended shape, so, can not discharge the ink composite drop in high-speed and continuous ground.Dynamic surface tension (σ when therefore, making bubble frequency be 10Hz ₁₀) with the dynamic surface tension (σ of bubble frequency when being 1Hz ₁) design is at 20～70mN/m, and σ ₁₀And σ ₁Difference d (=σ ₁₀-σ ₁) in above-mentioned certain limit, when in ink-jet recording method, using this ink composite, can obtain to discharge stable fine ink composite, and it can suppress the trace on the recording materials, thus the high quality record image is provided.

In addition, in the present invention, preferably, ink composite also comprises tensio-active agent.

According to the present invention, because ink composite also comprises tensio-active agent, so, can control the dynamic surface tension of ink composite at an easy rate, comprise that bubble frequency is the dynamic surface tension (σ of 10Hz ₁₀) and bubble frequency be the dynamic surface tension (σ of 1Hz ₁).

In addition, in the present invention, preferably, medium contains water.

According to the present invention, because medium contains water, so, can suppress trace to occur on the absorptivity recording materials, improve drying property.

In addition, in the present invention, preferably, medium contains at least a in gylcol ether and the polyalcohols.

According to the present invention, because medium contains the gylcol ether and the polyalcohols of at least a low-steam pressure, so, can obtain wetting effect and improve discharge stability.

In addition, in the present invention, preferably, tinting material comprises dyestuff.

According to the present invention, because tinting material comprises dyestuff, thereby can suppress the generation of spray nozzle clogging, improve and discharge stability.

In addition, in the present invention, preferably tinting material comprises pigment.

According to the present invention,, thereby can obtain to have the document image of good photostabilization and water resisting property because tinting material comprises pigment.

In addition, in the present invention, preferably, tinting material comprises the pigment with hydrophilic radical.

According to the present invention, tinting material comprises the pigment with hydrophilic radical.Whereby, can obtain to have the document image of good photostabilization and water resisting property.Also because pigment has hydrophilic radical, it can stably be dispersed in the aqueous ink composite.Therefore, can suppress the generation of spray nozzle clogging, so, the ink composite of discharging stability and obtaining to have the document image of good photostabilization and water resisting property do not reduced.

In addition, in the present invention, preferably, tensio-active agent comprises nonionic class tensio-active agent.

According to the present invention, because tensio-active agent comprises the nonionic class tensio-active agent of the ionogen influence that is difficult to be subjected to coexist, so above-mentioned bubble frequency is the dynamic surface tension (σ of 10Hz ₁₀) and bubble frequency be the dynamic surface tension (σ of 1Hz ₁) poor d (=σ ₁₀-σ ₁) can keep within the specific limits, and no matter whether added ionogen in the ink composite.

In addition, in the present invention, preferably, contain micelle-forming concentration or be higher than the tensio-active agent of micelle-forming concentration.

According to the present invention, contain micelle-forming concentration or be higher than the tensio-active agent of micelle-forming concentration.The surface tension that contains the solution of tensio-active agent is increased to micelle-forming concentration along with tensio-active agent and reduces, but basically in micelle-forming concentration or be higher than micelle-forming concentration and keep constant.Therefore, as mentioned above, owing to exist micelle-forming concentration or be higher than the tensio-active agent of micelle-forming concentration, so, might make full use of the effect of tensio-active agent, and to control bubble frequency with this tensio-active agent be the dynamic surface tension (σ of 10Hz ₁₀) and bubble frequency be the dynamic surface tension (σ of 1Hz ₁), it is remained unchanged basically, thereby can obtain having the ink composite of even character.

According to the present invention, because described pigment comprises the C.I. pigment Blue 15: 3 and the C.I. pigment Blue 15: at least a in 4, so, can obtain the ink composite of the good document image of a kind of cyan color emissivity.

In addition, in the present invention, preferably, described pigment comprises the pigment of at least a C.I. of being selected from pigment red 122, C.I. Pigment red 209 and C.I. pigment violet 19.

According to the present invention, because described pigment comprises the pigment of at least a C.I. of being selected from pigment red 122, C.I. Pigment red 209 and C.I. pigment violet 19, so, can obtain the ink composite of the good document image of magenta color emissivity.

In addition, in the present invention, preferably, described pigment comprises the pigment of at least a C.I. of being selected from Pigment Yellow 73 74, C.I. pigment yellow 13 8, C.I. Pigment Yellow 73 150 and C.I. Pigment Yellow 73 180.

According to the present invention, because described pigment comprises the pigment of at least a C.I. of being selected from Pigment Yellow 73 74, C.I. pigment yellow 13 8, C.I. Pigment Yellow 73 150 and C.I. Pigment Yellow 73 180, so, can obtain the ink composite of the good document image of a kind of yellow color emissivity.

In addition, in the present invention, preferably, described pigment comprises carbon black.

According to the present invention, because described pigment comprises carbon black, so, can obtain the ink composite of the good document image of black color emissivity.

It is a kind of by the recording method of ink composite attached to document image on the recording materials that the present invention also provides, and the ink composite of this method is any in the invention described above ink composite.

According to the present invention, make ink composite attached on the recording materials and the recording method of document image, adopted any in the invention described above ink composite, provide the high quality record image thereby can stablize.

The present invention also provides a kind of recording method of document image, this method is by exerting pressure to ink composite, the ink composite drop is discharged, attached on the recording materials and the recording method of document image, wherein used ink composite is any in the invention described above ink composite with drop.

According to the present invention, exert pressure to ink composite, make the ink composite drop discharge and drop attached on the recording materials and the recording method of document image, it is ink-jet recording method, adopted any in the invention described above ink composite, discharged and provide the high quality document image thereby can stablize.

In addition, in the present invention, preferably, this ink composite has used at least a following ink composite: wherein said pigment comprises the C.I. pigment Blue 15: 3 and the C.I. pigment Blue 15: at least a ink composite in 4, wherein said pigment comprises the ink composite of the pigment of at least a C.I. of being selected from pigment red 122, C.I. Pigment red 209 and C.I. pigment violet 19, and wherein said pigment comprises the ink composite of at least a C.I. of being selected from Pigment Yellow 73 74, C.I. pigment yellow 13 8, C.I. Pigment Yellow 73 150 and C.I. Pigment Yellow 73 180 pigment.

According to the present invention, this ink composite uses the ink composite of the good document image of the ink composite of the good document image of at least a ink composite, the magenta color emissivity that can access the good document image of cyan color emissivity and yellow color emissivity.Therefore, by the above-mentioned three kinds of ink composites that superpose, can realize highdensity black recording image.Therefore, use above-mentioned three kinds of ink composites can present various colors, thereby can provide color emissivity good colored document image.

In addition, in the present invention, this ink composite uses at least a following ink composite: wherein said pigment comprises the C.I. pigment Blue 15: 3 and the C.I. pigment Blue 15: at least a ink composite in 4, wherein said pigment comprises at least a C.I. of being selected from pigment red 122, C.I. the ink composite of the pigment of Pigment red 209 and C.I. pigment violet 19, wherein said pigment comprises at least a C.I. of being selected from Pigment Yellow 73 74, C.I. pigment yellow 13 8, C.I. the ink composite of the pigment of Pigment Yellow 73 150 and C.I Pigment Yellow 73 180 and wherein pigment comprise the sooty ink composite.

According to the present invention, ink composite used at least a ink composite that can generate high-quality cyan document image, can generate the ink composite of the red document image of high-quality product, can generate ink composite and a kind of ink composite that can generate high-quality black recording image of the yellow document image of high-quality.Therefore, by the ink composite that can generate high-quality cyan document image, can generate the ink composite of the red document image of high-quality product and can generate 3 kinds of ink composites stacks of the ink composite of the yellow document image of high-quality, can realize highdensity black recording image.Therefore, adopt 4 kinds of ink composites that in above-mentioned 3 kinds of ink composites, add the ink composite that can generate high-quality black recording image, can present various colors, have the colored document image that generates good color thereby provide.

According to the present invention, owing to adopt this recording method document image, so, can obtain the high quality record image.

The present invention also provides a kind of printing ink group, and it comprises:

A kind of ink composite, wherein said pigment comprises the C.I. pigment Blue 15: 3 and the C.I. pigment Blue 15: at least a in 4;

A kind of ink composite, wherein said pigment comprise the pigment of at least a C.I. of being selected from pigment red 122, C.I. Pigment red 209 and C.I. pigment violet 19; With

A kind of ink composite, wherein said pigment comprise the pigment of at least a C.I. of being selected from Pigment Yellow 73 74, C.I. pigment yellow 13 8, C.I Pigment Yellow 73 150 and C.I Pigment Yellow 73 180.

According to the present invention, this printing ink group comprises a kind of ink composite that can generate high-quality cyan document image, a kind of ink composite and a kind of ink composite that can generate the yellow document image of high-quality that can generate the red document image of high-quality product.Therefore, by above-mentioned three kinds of ink composites stack being realized the document image of high-density black.That is it is good, to contain the printing ink group color balance of above-mentioned 3 kinds of ink composites.So, comprise by employing the printing ink group of above-mentioned 3 kinds of ink composites can showing various colors, thereby the colored document image that forms the high-quality color can be provided.

A kind of ink composite, wherein said pigment comprises the C.I. pigment Blue 15: 3 and the C.I. pigment Blue 15: at least a pigment in 4;

A kind of ink composite, wherein said pigment comprise the pigment of at least a C.I. of being selected from pigment red 122, C.I. Pigment red 209 and C.I. pigment violet 19;

A kind of ink composite, wherein said pigment comprise the pigment of at least a C.I. of being selected from Pigment Yellow 73 74, C.I. pigment yellow 13 8, C.I. Pigment Yellow 73 150 and C.I Pigment Yellow 73 180; With

A kind of ink composite, wherein said pigment comprises carbon black.

According to the present invention, the printing ink group comprises a kind of ink composite that can generate high-quality cyan document image, a kind ofly can generate the ink composite of the red document image of high-quality product, a kind of ink composite and a kind of ink composite that can generate high-quality black recording image that can generate the yellow document image of high-quality.Therefore, with the above-mentioned ink composite that can generate high-quality cyan document image, can generate the ink composite of the red document image of high-quality product and can generate 3 kinds of ink composites such as ink composite of the yellow document image of high-quality superimposed, can realize highdensity black recording image.Therefore, comprise that the color balance of printing ink group of above-mentioned 3 kinds of compositions is good.Therefore, use the printing ink group that comprises 4 kinds of ink composites that in above-mentioned 3 kinds of ink composites, adds the ink composite that can generate high-quality black recording image can show various colors, thereby can provide color emissivity good colored document image.

The present invention also provides a kind of ink gun, and it comprises:

Store the ink tank of above-mentioned any ink composite of the present invention;

Ink cartridge, its relief outlet with discharge ink composite drop also receives the ink composite from ink tank;

To applying the piezoelectric element that voltage produces deformation, this piezoelectric element is equipped with at least in a part of ink cartridge, thereby the ink composite in print cartridge is exerted pressure; With

Apply the electrode of voltage toward piezoelectric element.

According to the present invention, ink gun has stored any ink composite of the present invention by ink tank, and holds the ink composite of supplying with from ink tank by having the print cartridge of discharging ink composite drop relief outlet; Apply voltage by electrode to piezoelectric element; Exert pressure toward the ink composite in the print cartridge by piezoelectric element, this piezoelectric element produces deformation with the voltage that applies and is provided at least a portion print cartridge.Therefore, obtain a kind of piezoelectric ink-jet head,, discharge the ink composite drop from relief outlet according to the voltage that is applied on the piezoelectric element.Also have, because ink tank has stored any ink composite of the present invention, so the ink composite drop can stably be discharged from relief outlet.As the ink gun adopting, the piezoelectric ink jet recording unit that can realize having high reliability.

The present invention also provides a kind of ink gun, and it comprises:

Store the ink tank of any ink composite of the invention described above;

Print cartridge, its relief outlet with discharge ink composite drop also receives the ink composite from ink tank;

The Heating element that at least a portion ink cartridge, is equipped with, this element is suitable for heating the ink composite in the print cartridge, so that produce bubble therein, thereby exerts pressure toward ink composite; With

Be used for applying voltage and the electrode that is equipped with toward Heating element.

According to the present invention, ink gun has stored any ink composite of the present invention by ink tank; Hold the ink composite of supplying with from ink tank by print cartridge with the relief outlet of discharging the ink composite drop; Apply voltage by electrode to Heating element; By the ink composite in the Heating element heating print cartridge that at least a portion print cartridge, is equipped with,, thereby exert pressure toward ink composite with the generation bubble.Therefore, obtained hot ink jet type ink gun, it discharges the ink composite drop according to the voltage that puts on Heating element from relief outlet.Also have, because ink tank has stored any ink composite of the present invention, so the ink composite drop can stably be discharged from relief outlet.As the ink gun adopting, the hot ink jet type ink-jet recording device that can realize having high reliability.

The present invention also provides ink composite drop that a kind of handle discharges by piezoelectric ink-jet head attached to the document image that writes down on the recording materials.

According to the present invention, because the ink composite drop of discharging by piezoelectric ink-jet head forms document image attached on the recording materials, so, piezoelectric ink-jet head can be as above-mentioned stable discharge ink composite drop, thereby can stably obtain the high quality record image.

The present invention also provides a kind of ink composite drop of hot ink jet type ink gun discharge attached to the document image that is write down on the recording materials.

According to the present invention, because the ink composite drop that hot ink jet type ink gun is discharged attached on the recording materials, forms document image, so, hot ink jet type ink gun can be discharged the ink composite drop as stablize above-mentionedly, thereby, can stably obtain the high quality record image.

Description of drawings

To more clearly explain purpose of the present invention, characteristics and advantage from the following detailed description and accompanying drawing.

Fig. 1 is the exploded perspective view that the ink gun structure of the present invention's the 2nd embodiment is simplified;

Fig. 2 is the part enlarged view of ink gun top board structure shown in Figure 1;

Fig. 3 is the cross-sectional view from the ink gun shown in Figure 1 of print cartridge bearing of trend observation;

Fig. 4 is the exploded perspective view that the ink gun structure of the 3rd embodiment of the present invention is simplified;

Fig. 5 is the partial plan of ink gun structure shown in Figure 4; With

Fig. 6 is ink composite drop 61 is discharged state from print cartridge a schematic cross section.

Embodiment

With reference to following accompanying drawing, describe the preferred embodiments of the invention in detail.

The ink composite of the present invention's the 1st embodiment comprises a kind of tinting material and at least as the organic solvent of medium, measuring temperature is 24～26 ℃ of dynamic surface tensions that adopt maximum bubble method to measure down, static surface tensions with in 24～26 ℃ of following mensuration of temperature, satisfy the relation of following formula (1):

0≤[dynamic surface tension (mN/m)]-[static surface tension (mN/m)]≤7 (mN/m) (1)

Below will illustrate and measure the maximum bubble method that dynamic surface tension uses.

Maximum bubble method is the capillary method of a kind of mensuration, this method is to insert tubule in liquid, produce bubble by the tubule front end, thereby in liquid, form liquid-gas interface, when inner with the outside pressure reduction of bubble reaches maximum, promptly when the radius of bubble equals the tubule radius r, measure pressure difference Δ P, then, obtain the method for surface tension σ by this value.Surface tension σ obtains from following formula (A).

σ＝ΔP·r/2 (A)

Bubble frequency is the number of bubbles that time per unit produces, and by changing bubble frequency, can obtain capillary dynamic change, i.e. dynamic surface tension.By measuring dynamic surface tension, can estimate the variation of the dynamic property of liquid.In this embodiment, in being 0.5～35Hz scope, bubble frequency measures dynamic surface tension.

For example, adopt the measuring method as static surface tension such as the ring method be called di Nuit method or suspension board method (suspended plate method).In this embodiment, adopt the suspension board method to measure static surface tension.

The ink composite of the present embodiment is suitable for ink-jet recording method.In this ink-jet recording method, exert pressure toward ink composite, the ink composite drop is discharged, with such drop attached on the recording materials and document image.

In the ink-jet recording device that adopts the ink-jet recording method document image, when discharging the ink composite drop continuously, by the relief outlet that the print cartridge front end in the ink gun is provided with, the new surface that produces ink composite incessantly, thereby the ink composite quick travel, the influence of dynamic surface tension is big.On the other hand, in print cartridge, after ink composite is discharged, because wicking action, ink composite is discharged from ink tank, and output is corresponding to the volume that reduces because of discharge, thereby ink composite slowly moves, can think static, thereby static surface tension has very big influence.So,,, be necessary to consider the balance of dynamic surface tension and static surface in order to reach the stable discharge of ink composite drop because dynamic surface tension and static surface tension both exert one's influence to discharge.The ink composite drop is attached on the recording materials and during document image, and ink composite drops on the moment quick travel of recording materials at drop, but slack-off gradually afterwards.When recording materials were the absorptivity recording materials, ink composite was penetrated in the recording materials.That is, because surface tension becomes static surface tension by dynamic surface tension, so; the difference of dynamic surface tension and static surface tension is big; then require ink composite longer time of drying on recording materials, thereby cause producing trace or cause undue infiltration, cause back side ink bleed.

As mentioned above, the ink composite of the present embodiment satisfies following formula (1) by make its dynamic surface tension measured according to maximum bubble method and the static surface tension of measuring in 24～26 ℃ of temperature in measuring 24～26 ℃ of temperature, promptly the dynamic surface tension of measuring in 24～26 ℃ of temperature designs in certain certain scope with the difference of static surface tension, thereby can obtain a kind of ink composite that is applied in the ink-jet recording method, said composition demonstrates good discharge stability, and trace occurs on the inhibition recording materials, thereby provide the high quality record image.Therefore, in ink-jet recording method, use the ink composite of the present embodiment, might reach stable and discharge, and the high quality document image stably is provided.

The reason of restriction the present embodiment ink composite scope of design below will be described.

If the dynamic surface tension of measuring in 24～26 ℃ of temperature (mN/m) surpasses 7mN/m with the difference of static surface tension (mN/m), the balance of dynamic surface tension and static surface tension worsens, and drop then can not be stablized discharge.And the drying of recording materials needs the time and produces trace, thereby makes the picture quality variation.Therefore, the scope of selection will be equal to or less than 7mN/m.

If the dynamic surface tension of measuring in 24～26 ℃ of temperature (mN/m) and the difference of static surface tension (mN/m) are less than 0mN/m, static surface tension uprises, reduced the wettability of ink composite to the assembly of formation ink gun, therefore, it is difficult that the ink composite filling ink cartridges becomes.So the scope of selection should be equal to or greater than 0mN/m.

The static surface tension that contains the ink composite of at least a tinting material and a kind of organic solvent is preferably 20～50mN/m, more preferably 20～45mN/m.

When static surface tension during less than 20mN/m, it is too high that perviousness becomes, and causes ink composite transverse dispersion on the absorptivity recording materials, thereby the image outline that generates is unintelligible.And static surface tension is when surpassing 50mN/m, reduce toward the perviousness of recording materials, thereby drying property reduces.In addition, the wettability of ink composite and print cartridge inwall reduces, and hinder ink composite and supply with print cartridge, and make the ink composite filling ink cartridges become difficult, thereby the ink composite drop can not be stablized discharge.Therefore, the scope of selection is 20～50mN/m.

At least the viscosity that contains the ink composite of a kind of tinting material and organic solvent preferably is equal to or less than 20mPa.s when measuring 25 ℃ of temperature, more preferably be equal to or less than 15mPa.s.When using in ink-jet recording method, when ink composite viscosity surpassed 20mPa.s, the ink composite drop can not be stablized discharge.Therefore, the scope of selection is equal to or less than 20mPa.s.

Except tinting material and organic solvent, the ink composite of the present embodiment preferably contains the water as medium.Such composition can be suppressed at and occur trace on the recording materials, improves drying property.

The content of water is preferably 30～95 weight % in the ink composite, more preferably 30～85 weight %.When water-content during less than 30 weight %, the amount of organic solvent increases, the water-soluble stabilization difficulty that maybe can be dispersed in the easer in the water.In addition, when organic solvent composition excessively increased, viscosity obviously increased, and finally exceeded the suitable range of viscosities of ink composite.In addition, when water-content surpassed 95 weight %, the amount of organic solvent was very few, thereby can not keep the wettability of ink composite.Therefore, the scope of its selection is 30～95 weight %.

Tinting material can be dyestuff, pigment or its mixture.Dyestuff or pigment can be the materials that contains dyestuff or pigment, or adhere to the material of dyestuff or pigment on it.

Can suppress to stop up as tinting material by the use dyestuff, thereby improve the stability of discharging.By adopting pigment also can obtain the good document image of photostabilization and water resisting property as tinting material.

In order in the color ink-jetting record method, to reproduce various colors, can use the ink composite of 3 kinds of colors, they are cyan (being abbreviated as C), magenta (being abbreviated as M) and yellow (being abbreviated as Y), can show various colors by these ink composites are mixed.But,, therefore, use the ink composite of black (being abbreviated as B) to show black usually owing to be difficult to reproduce black by mixing 3 kinds of colors.The color of the tinting material that contains by change can obtain the ink composite of cyan, magenta, yellow or black.

Dyestuff is had no particular limits, but when ink composite contained water, it was preferred using water-soluble dyes such as matching stain, substantive dyestuff, reactive dyestuffs or food dye.In these water-soluble dyes, preferably use water resisting property, photostabilization or security excellent dye.

The specific examples of dyestuff can be enumerated following dyestuff, but dyestuff is not limited to these examples.In following example, with color index (being called for short C.I.) expression dyestuff.

The dyestuff that uses in the cyan ink composition comprises matching stain, for example C.I. Acid Blue 7,9,29,45,92 and 249; Substantive dyestuff is as C.I. sun blue 1,2,6,15,22,25,71,76,79,86,90,98,163,165,199 and 202; Reactive dyestuffs are as C.I. Reactive blue 1,2,7,14,15,23,32,38,41,63,80 and 95 etc.In these dyestuffs, preferably use at least a C.I. of being selected from Acid Blue 7 and 9 and the dyestuff of C.I. sun blue 199.

Spendable dyestuff comprises matching stain in magenta ink compositions, as C.I. azogeramine, 8,13,14,18,26,27,35,37,42,52,82,87,89,92,97,106,111,114,115,134,186,249,254 and 289; Substantive dyestuff, directly red 1,4,9,13,17,20,28,31,39,80,81,83,89,225 and 227 as C.I., C.I.

direct orange

26,29,62 and 102; Reactive dyestuffs are as C.I. reactive red 1,14,17,25,26,32,37,44,46,55,58,60,66,74,79,96,97,141,147,180 and 181 etc.In these dyestuffs, preferably use at least a C.I. of being selected from Xylene Red 52 and 289 and the dyestuff of C.I. reactive red 58,141 and 180.

Spendable dyestuff comprises matching stain in the Yellow ink composition, as C.I. turmeric yellow 1,7,17,23,42,44,79 and 142; Substantive dyestuff is as C.I. direct yellow 1,12,24,26,33,44,50,86,120,132,142 and 144; Reactive dyestuffs are as C.I. reactive yellow 1,5,11,13,14,20,21,22,25,40,47,51,55,65 and 67 etc.In these dyestuffs, preferably use at least a C.I. of being selected from turmeric yellow 17 and 23 and direct yellow 86 the dyestuff of C.I..

Spendable dyestuff comprises food dye in black ink composition, as C.I. edible black 2; Substantive dyestuff directly deceives 19,22,32,38,51,56,71,74,75,77,154,168 and 171 as C.I.; Reactive dyestuffs are as C.I. reactive black 3,4,7,11,12 and 17 etc.In these dyestuffs, preferably use directly black 154 dyestuff of a kind of C.I. edible black 2 and C.I. at least.

Use these dyestuffs at normal temperatures in the scope of stable meltable.Because every kind of such scope of dyestuff has nothing in common with each other, so dyestuff content is not particularly limited in the ink composite, but is preferably 0.1～10 weight %.

As for pigment, can use any can dispersive in solution pigment, be preferred but use photostabilization or the good pigment in security aspect.

The specific examples of pigment can be enumerated following pigment, but pigment is not limited to these.In following example, with color index (C.I.) number expression pigment.

The pigment example that uses in cyan ink composition comprises C.I. pigment blue 1,2,15,16,17,21,22,60 and 64 etc.

The pigment example that uses in magenta ink compositions comprises C.I.

Pigment red

2,3,5,16,23,31,49,57,63,122 and 209 and C.I. pigment violet 19 etc.

The pigment example that uses in the Yellow ink composition comprises C.I Pigment Yellow 73 1,2,3,5,12,74,138,150 and 180 etc.

The pigment example that uses in black ink composition comprises carbon black, as thermally oxidized black, furnace black, thermal black or dim etc.

In these pigment, the preferred C.I. pigment Blue 15 that uses in cyan ink composition: 3 and pigment Blue 15: at least a pigment in 4.For magenta ink compositions, preferably use the pigment of a kind of C.I. of being selected from pigment red 122, C.I. Pigment red 209 and C.I. pigment violet 19 at least.And, preferably use the pigment of a kind of C.I. of being selected from Pigment Yellow 73 74, C.I. pigment yellow 13 8, C.I. Pigment Yellow 73 150 and C.I. Pigment Yellow 73 180 at least for the Yellow ink composition.For black ink composition, preferably use at least a above-mentioned sooty pigment that is selected from.

By using these pigment can obtain to realize the ink composite of the document image that color emissivity of all kinds is good.When printing ink group that cyan, magenta and 3 kinds of ink composites of xanchromatic of using these pigment are combined into, by this 3 member ink sets compound stack, can obtain high-density black document image, it approaches the document image that forms with black ink composition.Therefore, do not use black ink composition can show colour yet.

When this ink composite contained water, pigment optimization had one or more hydrophilic radicals, and these genes are selected from for example carboxyl, hydroxyl, amino and sulfonic group etc.Such hydrophilic radical can directly be added on the surface of pigments by chemical modification, or imports by hydrophilization with the polymkeric substance coverage pigment surface with such hydrophilic radical.Such hydrophilic radical can also be a salt.

But the pigment stable dispersion with hydrophilic radical is in aqueous ink composite.Therefore, the pigment that has hydrophilic radical by use is as tinting material, and the generation that can suppress to stop up is discharged stability and obtained photostabilization and the good document image of water resisting property thereby do not damage.

At normal temperatures, but in the scope of stable dispersion, use these pigment.Because such scope of every kind of pigment has nothing in common with each other, so pigment content is not particularly limited in the ink composite, but 0.1～10 weight % preferably.

The specific examples of organic solvent for example, can be enumerated amides, as dimethyl formamide or N,N-DIMETHYLACETAMIDE; Polyalcohols is as polyoxyethylene glycol, polypropylene glycol, ethylene glycol, glycol ether, thiodiglycol (thiodiglycol), propylene glycol, triglycol, 1,5-pentanediol, 1,4-butyleneglycol, 1,2-hexylene glycol, 1, ammediol, glycerine and 1,2,6-hexanetriol; The ethers of polyvalent alcohol is as glycol ethers (glycol ether), as methyl glycol, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, ethyl carbitol, triglycol monobutyl ether, propylene glycol monoethyl ether, Tetraglycol 99 monomethyl ether and Rokafenol F 1 etc.; Sulfocompound is as tetramethylene sulfone or dimethyl sulfoxide (DMSO) etc.; Nitrogenous compound is as 2-Pyrrolidone, N-Methyl pyrrolidone or ε-Ji Neixianan etc.; Oxygenatedchemicals is as gamma-butyrolactone etc.; The polyfunctional compound, as dimethylaminoethanol, DEAE diethylaminoethanol, trolamine or morpholine etc., but organic solvent is not limited to such example.

In these organic solvents, preferably use glycol ethers or polyalcohols, because such solvent has low vapour pressure, when containing such solvent in the ink composite, obtained wetting effect, discharge stability thereby improve.In glycol ethers, more preferably use butylcarbitol, propylene glycol monobutyl ether, triglycol monobutyl ether or Tetraglycol 99 monobutyl ether as organic solvent, their vapour pressures in the time of 25 ℃ are 0.01 mmhg or lower, and have good wetting effect.In polyvalent alcohol, more preferably use glycerine, 1,2-hexylene glycol or 1, the 5-pentanediol, their vapour pressures in the time of 25 ℃ are 0.01 mmhg or lower, and have good wetting effect.

The content of organic solvent is preferably 3～70 weight % in the ink composite, more preferably 3～50 weight %.When organic solvent during less than 3 weight %, can cause ink composite dry rapidly, be difficult to keep wettability.And when organic solvent surpassed 70 weight %, easer water-soluble or that water is not dispersed can not stably exist.In addition, depend on the kind of solvent for use, viscosity demonstrates tangible increase, and exceeds the proper viscosity scope of ink composite.Therefore, the scope of selection is 3～70 weight %.But, when ink composite with water during as main ingredient, its content is preferably 3～40 weight %, more preferably 3～30 weight %.But when ink composite during as main ingredient, when organic solvent surpasses 40 weight %, although depend on the kind of used tinting material, still causes the reduction of printing quality and the lengthening of time of drying with water.Therefore, the scope of selection is 3～40 weight %.

The ink composite of the present embodiment preferably further comprises tensio-active agent.Such formation can easily be controlled above-mentioned dynamic surface tension and static surface tension.

Tensio-active agent can be any or its combination of non-ionic species tensio-active agent, anionic species tensio-active agent, cationic tensio-active agent.The type of tensio-active agent as nonionic, positively charged ion or anion surfactant, should be selected according to the ionogen kind that contains in the ink composite.For example, if ink composite contains the anionic property material, then use nonionic class or anionic species tensio-active agent.In these tensio-active agents, nonionic class tensio-active agent is preferred, because it is not vulnerable to the electrolytical influence that coexists, the difference of dynamic surface tension and static surface tension is remained in the predetermined scope, and no matter whether ink composite has added ionogen.

The specific examples of nonionic class tensio-active agent can enumerate with following general formula (I), (II), (III), (IV), (V) and (VI) tensio-active agent etc. of expression, but nonionic class tensio-active agent is not limited to these examples.

HO(CH ₂CH ₂O) _p(CH ₂CH ₂CH ₂O) _q(CH ₂CH ₂O) _rH (V)

In general formula (I), m represents 0～30 integer or mark; N represents 0～30 integer or mark; Integer or mark m and n and (m+n) expression 0～30.

In general formula (II), k represents 11～13 integer or mark; L represents 3～30 integer or mark.

In general formula (III), h represents 0～11 integer or mark; I represents 0～11 integer or mark; J represents 3～50 integer or mark; Integer or mark h and i and (h+i) expression 9～11.

In general formula (IV), w represents 0～11 integer or mark; X represents 5～9 integer or mark; Y represents 2.5～5 integer or mark; Z represents 0～9 integer or mark; Integer or mark w and z and (w+z) expression 9～11.

In logical formula V, p represents 0～78 integer or mark; Q represents 2～15 integer or mark; R represents 0～18 integer or mark.

In general formula (VI), s and t and (s+t) expression 1～30 integer or mark, u and v and (u+v) represent 1～10 integer or mark.

In ink composite, preferably contain micelle-forming concentration or be higher than the tensio-active agent of micelle-forming concentration.The surface tension that contains the solution of tensio-active agent is increased to micelle-forming concentration along with tensio-active agent and reduces, and keeps constant basically but be higher than micelle-forming concentration.Therefore, when using above-mentioned micelle-forming concentration or being higher than the tensio-active agent of micelle-forming concentration, can give full play to the effect of tensio-active agent, and make dynamic surface tension and static surface tension keep steady state value basically, thereby the ink composite that acquisition has even performance by tensio-active agent control.

Although the micelle-forming concentration difference of various tensio-active agents, but for any nonionic class tensio-active agent, anionic species tensio-active agent and cationic tensio-active agent, its micelle-forming concentration is about 0.001～3 weight % (a mensuration temperature: 25 ℃).

When adopting pigment in the tinting material, the ink composite of the present embodiment preferably contains resin glue.By containing resin glue, can prevent that pigment from peeling off from recording materials.

As resin glue, can use one or more to be selected from resins such as vibrin, acrylic resin, styrene-propene acid copolymer resin and polyester-acrylic copolymer resin.

Except tinting material, organic solvent, water, tensio-active agent and resin glue, the ink composite of the present embodiment also can contain other additives, as mould inhibitor, pH value conditioning agent, sequestrant, rust-preventive agent (antirusting agent) or UV light absorber.

For mould inhibitor, it is preferred using Sodium dehydroacetate, Sodium Benzoate or sodium sorbate (sodium sorbinate) etc.

For the pH regulator agent, it is preferred using trolamine, sodium hydroxide, yellow soda ash, SODIUMNITRATE or saltpetre etc.

For example, use 0.5～15 weight % tinting material, 3～70 weight % organic solvents, 29～95 weight % water and 0.001～5 weight % tensio-active agent, can obtain a kind of ink composite, it contains a kind of tinting material and organic solvent at least, and it is that 24～26 ℃ of static surface tensions that adopt the dynamic surface tension of maximum bubble method mensuration down and measure under temperature is 24～26 ℃ satisfy the relation of following formula (1) in temperature.

Fig. 1 is the exploded perspective view that the structure of the ink gun 1 that constitutes the 2nd embodiment of the present invention is described, Fig. 2 is the partial enlarged drawing that constitutes ink gun 1 top board 10 structures shown in Figure 1.In order to simplify and easy to understand, drive electrode 13 shown in Figure 2 has omitted in Fig. 1.

Ink gun 1 is by constituting with lower member: the top board 10 that piezoelectric is made, and it has bottom wall portion 11 and a plurality of dividing plate 12; Cover plate 20, it is contained on the upper surface of dividing plate 12; Nozzle plate 30, it is located at an end of the dividing plate 12 with a plurality of relief outlets 31; Be located at the backplate (not shown) of dividing plate 12 the other ends; Be located at cover plate 20 tops and have the ink tank 50 of peristome 51.A plurality of dividing plates 12 are configured on the bottom wall portion 11 parallel to each other with predetermined spacing, constitute a plurality of print cartridges 40 by a plurality of dividing plates 12, bottom wall portion 11, cover plate 20, nozzle plate 30 and backplate (not shown).Cover plate 20, by shared inking road 21 Hes that communicate with print cartridge 40, the ink supply tube 22 that connects the peristome 51 of shared ink supply passage 21 and ink tank 50 forms.Ink tank 50 is storing the ink composite 60 of the 1st embodiment, and ink composite 60 offers each print cartridge 40 by shared ink supply passage 21.

As shown in Figure 2, on ink chamber 40 surfaces, form the drive electrode 13 that applies voltage toward a plurality of dividing plates 12 facing to the bottom wall portion 1 of top board 10 and a plurality of dividing plate 12.The piezoelectric that constitutes a plurality of dividing plates 12 is along direction polarization shown in the arrow 70, thereby a plurality of dividing plate 12 plays the effect of piezoelectric element.

The ink gun 1 of this spline structure is a piezoelectric ink-jet head, and according to the voltage that applies toward a plurality of dividing plates 12 as piezoelectric element, this piezoelectric ink-jet head can be discharged ink composite 60 drops from relief outlet 31.

The principle of work of ink gun 1 in the time of will illustrating from print cartridge 40 discharge ink composites 60 hereinafter.Fig. 3 is the cross-sectional view of the ink gun shown in Figure 11 seen from print cartridge 40 bearing of trends.Running condition in the time of will illustrating from print cartridge 40b discharge ink composite 60 hereinafter.

When voltage is not applied to the dividing plate 12a that constitutes print cartridge 40b and 12b, promptly between the print cartridge 40a drive electrode 13a of the drive electrode 13b of print cartridge 40b and contiguous print cartridge 40b, and when between the drive electrode 13c of print cartridge 40b drive electrode 13b and contiguous print cartridge 40b print cartridge 40c, not producing potential difference, be full of print cartridge 40b from the ink composite 60 that ink tank 50 provides by wicking action.Similarly, print cartridge 40a, 40c also are in the state that is full of ink composite 60.

When applying voltage, between drive electrode 13b and drive electrode 13a, and between drive electrode 13b and drive electrode 13c, produced potential difference, thereby dividing plate 12a and the 12b of past formation print cartridge 40b have applied voltage toward drive electrode 13a and 13c.This voltage produces electric field along arrow 71 and 72 directions respectively in dividing plate 12a and 12b, such electric field produces deformation in dividing plate 12a that constitutes print cartridge 40b and 12b, thereby produces the distortion of projection in print cartridge 40b side.Therefore, produced pressure wave, the ink composite 60 of filling in the print cartridge 40 has been applied very big pressure, thereby discharged ink composite 60 drops from relief outlet shown in Figure 1 31.

When stopping when drive electrode 13a and 13c apply voltage, dividing plate 12a and 12b get back to original shape, recover the original volume of print cartridge 40, thereby provide ink composite corresponding to the volume that recovers by shared ink supply passage 21 shown in Figure 1 from ink tank 50, print cartridge 40b gets back to the original state of extending oil ink composition 60.

As mentioned above, because ink tank 50 has stored the ink composite 60 of the 4th embodiment, such ink composite 60 is supplied with print cartridge 40, and discharges with drop from relief outlet 31, so the ink gun 1 of embodiment can stably be discharged ink composite 60 drops from relief outlet 31.As the ink gun adopting, the piezoelectric ink jet recording unit that can realize having high reliability can be stablized and obtains the high quality record image.

In the present embodiment, the dividing plate 12 usefulness piezoelectrics that constitute print cartridge 40 are made, and play the effect of piezoelectric element, but such structure are not limited, can also make the dividing plate that constitutes print cartridge with non-piezoelectric material, also can at the inner or outside installation piezoelectric element of dividing plate.

Fig. 4 is the STRUCTURE DECOMPOSITION stereographic map that schematic illustration constitutes the ink gun 2 of the present invention's the 3rd embodiment, and Fig. 5 is the partial plan layout of ink gun 2 structures shown in Figure 4.In order to simplify and easy to understand, cover plate 20 shown in Figure 4 and ink tank 50 have dispensed in Fig. 5.The ink gun 2 of the present embodiment is similar to the ink gun 1 of the 2nd embodiment, therefore with the corresponding parts of identical numeral, explains and also will omit.

Should note, top board 100 comprises substrate 101 Hes, a plurality of dividing plates 102 that dispose parallel to each other with predetermined interval on substrate 101 and lip-deep well heater 103 Hes as heating element that are installed in the face of the print cartridge 40 of substrate 101, past well heater 103 applies the drive electrode 104,105 of voltage.

The ink gun 2 of this spline structure is hot ink jet type ink gun, and it can discharge ink composite 60 drops from relief outlet 31 according to the voltage that applies toward the well heater 103 as heating element.

Hereinafter, will the principle of work of ink gun 2 from print cartridge 40 discharge ink composites 60 time be described.Fig. 6 is the drop 61 of ink composite 60 is discharged in explanation from print cartridge 40 state graph.Fig. 6 illustrates the cross-section structure of ink gun 2 along section line I-I.

When toward well heater 103 when applying voltage, its state is similar to the state that the dividing plate 12 in the 2nd embodiment ink gun 1 not applies voltage, and print cartridge 40 is in the state of having filled ink composite 60.

When

drive electrode

104 and 105 applied voltage toward well heater 103, well heater 103 produced heat, has heated the ink composite 60 of filling in the print cartridge 40, produces bubble 62.Therefore, produce pressure wave, the ink composite 60 of filling in the print cartridge 40 imposes severe pressure, thereby the drop 61 that makes ink composite 60 is from relief outlet 31 discharges.

When termination applies voltage toward well heater 103, ink composite 60 in the print cartridge 40 is cooled, bubble 62 disappears, supply ink composites 60 by shared ink supply passage 21 shown in Figure 4 from ink tank 50, its volume is corresponding to the volume that recovers, and print cartridge 40 is got back to the original state of having filled ink composite 60.

Identical with the ink gun 1 of the 2nd embodiment, the ink gun 2 of the present embodiment, because ink tank 50 has stored the ink composite 60a of the 4th embodiment, and such ink composite 60a supplies with print cartridge 40, and discharge with drop 61a from relief outlet 31, therefore, can stably discharge the drop 61a of ink composite 60 from relief outlet 31.As the ink gun adopting, can realize having the hot ink jet type ink-jet recording device of high reliability, and can stablize the high quality record image is provided.

Embodiment

To further illustrate the present invention by embodiment below, but the present invention is not subjected to the restriction of these embodiment.In these embodiments, image recording is also referred to as and prints or printing.

＜ink composite 〉

In the process of preparation ink composite, as shown in table 1 change of content of the kind of tinting material, organic solvent and tensio-active agent and quantity and resin glue and water, with the ink composite of the comparative example 1～4 of the ink composite of the embodiment 1～7 of the relational expression (1) that obtains to satisfy essential condition of the present invention and discontented unabridged version invention relational expression (1).In table 1, the unit of each hurdle value represents that with weight part each ink composite total amount of embodiment 1～7 and comparative example 1～4 is 100 weight parts.In addition, in table 1, TEGBE represents the triglycol monobutyl ether; PEG400 represents that molecular weight is 400 polyoxyethylene glycol; The tensio-active agent that fluorinated surfactant 1 expression is represented with following chemical formula (VII); The tensio-active agent that fluorinated surfactant 2 expressions are represented with following chemical formula (VIII):

In embodiment 1～7 and comparative example 1～4, measure the dynamic surface tension and the static surface tension of ink composite in the following way.

＜dynamic surface tension 〉

When bubble frequency 0.5～35Hz, (BP-4: produced by Kyowa KaimenKagaku Co.) measures with tensiometer.

＜static surface tension 〉

(CBVP-A3: produced by Kyowa Kaimen Kagaku Co.) measures with the static surface tension meter.

Table 2 illustrates the measured value of each the ink composite dynamic surface tension of embodiment 1～7 and comparative example 1～4 and static surface tension, in order to the d value of following formula (B) expression with survey periodic temperature and bubble frequency.

D (mN/m)=[dynamic surface tension (mN/m)]-[static surface tension (mN/m)] (B)

Table 1 (wherein R is a surplus)

Composition			Embodiment							Comparative example
			Embodiment							Comparative example				1	2	3	4	5	6	7	1	2	3	4
				Dyestuff	C.I. sun blue 199	2.5								1	2	3	4	5	6	7	1	2	3	4
	C.I. pigment Blue 15: 3			Dyestuff	C.I. sun blue 199	2.5								3
	C.I. pigment Blue 15: 3			C.I. pigment Blue 15: 4			3							3
	C.I. pigment red 122			C.I. pigment Blue 15: 4			3									5
	C.I. pigment red 122			C.I. Pigment Yellow 73 74					4							5
	C.I. Pigment Yellow 73 180			C.I. Pigment Yellow 73 74					4									4
	C.I. Pigment Yellow 73 180			Carbon black							5							4							5
	C.I. pigment blue 17			Carbon black							5									2					5
	C.I. pigment blue 17			C.I. Pigment red 58									3							2
	C.I. pigment yellow 13			C.I. Pigment red 58									3									2
	C.I. pigment yellow 13					Glycol ether	8	8	8	5	5	8	8									2		2	5	20	10
Glycerol	5	7	8			Glycol ether	8	8	8	5	5	8	8	10	8	8	9	5	5	17	10			2	5	20	10
Glycerol	5	7	8			1, the 5-pentanediol			2	5	2	2	5	10	8	8	9	5	5	17	10		2	18	5
TEGBE	8	8	8			1, the 5-pentanediol			2	5	2	2	5	5	5	3	6	4			8		2	18	5
TEGBE	8	8	8			PEG400		1						5	5	3	6	4			8	10	15	15	10
		General formula (I) (m+n=10)				PEG400		1						1								10	15	15	10
		General formula (I) (m+n=10)		General formula (II) (k=11～13,1=15)			1				1.0			1
		General formula (III) (h+i=9～11, j=9)		General formula (II) (k=11～13,1=15)			1				1.0					1.5
		General formula (III) (h+i=9～11, j=9)		General formula (IV) (w+z=9～11, x=9, y=5)					1.5							1.5
		Logical formula V (p=12, q=8, r=4)		General formula (IV) (w+z=9～11, x=9, y=5)					1.5									1
		Logical formula V (p=12, q=8, r=4)		Fluorinated surfactant 1								1						1					0.5
		Fluorinated surfactant 2		Fluorinated surfactant 1								1									1.5		0.5	1	0.5
		Fluorinated surfactant 2		Resin glue		Vibrin	Do not have	1	1.5	2	1	1.5	1								1.5	1	1.5	1	0.5	2	2
Water			R	Resin glue		Vibrin	Do not have	1	1.5	2	1	1.5	1	R	R	R	R	R	R	R	R	1	1.5	R	R	2	2

Table 2

	Embodiment							Comparative example
	Embodiment							Comparative example				1	2	3	4	5	6	7	1	2	3	4
	Dynamic surface tension (mN/m)	31.9	31.9	34.5	34.7	34.4	34.8	34.6	31.4	29.5	29.5	1	2	3	4	5	6	7	1	2	3	4	28.6
Static surface tension (mN/m)	Dynamic surface tension (mN/m)	31.9	31.9	34.5	34.7	34.4	34.8	34.6	31.4	29.5	29.5	27.9	27.8	30.4	30.8	30.4	31.0	30.1	23.3	20.5	20.5	20.4	28.6
Static surface tension (mN/m)	d(mN/m)	4	4.1	4.1	3.9	4	3.8	4.5	8.1	9	9	27.9	27.8	30.4	30.8	30.4	31.0	30.1	23.3	20.5	20.5	20.4	8.2
The mensuration temperature (℃)	d(mN/m)	4	4.1	4.1	3.9	4	3.8	4.5	8.1	9	9	25.6	25.6	25.3	25.6	25.1	25.0	24.8	24.7	25.7	24.8	24.6	8.2
The mensuration temperature (℃)	Measure bubble frequency (Hz)	15	14	14	15	16	16	15	15	16	16	25.6	25.6	25.3	25.6	25.1	25.0	24.8	24.7	25.7	24.8	24.6	16

Each ink composite of embodiment 1～7 that obtains and comparative example 1～4 is filled in the ink tank of ink-jet recording device, this ink-jet recording device obtains through transformation with commercially available ink-jet recording device (AJ2000: produced by SharpKabushiki Kaisha), with the print speed of 7 pages of A4 paper of per minute, in the plain copying paper of producing by Sharp Kabushiki Kaisha (trade(brand)name: SF4AM3) upward print continuously with print density 5%.In this test, when the ink tank sky time recharge ink composite, print continuously up to can not discharge from nozzle because of the ink composite drop can not print again till, counting is up to the paper quantity of printing fully at the moment, obtain printable paper number, as discharging stability evaluation index.If printable paper number surpasses 200, be assessed as (zero), if the paper number is 150～200, be assessed as better (△), if be less than 150, be assessed as poor (*).

In addition, each ink composite of embodiment 1～7 and comparative example 1～4 is filled in the ink tank of ink-jet recording device, ink-jet recording device is that commercially available ink-jet recording device (AJ2000: produced by SharpKabushiki Kaisha) obtains through transformation, in the plain copying paper of producing by Sharp Kabushiki Kaisha (trade(brand)name: SF4AM3) go up the specific pattern of printing, the image that is formed for estimating.The evaluation map picture was placed after one day, if when not having trace, pattern line-width is decided to be 100, measures the pattern line-width of each evaluation map picture and obtains relative value, as the index of assess image quality.If the live width relative value is less than 150 and almost do not have trace, the result just is chosen as (zero), if relatively live width is 150～250, some traces is arranged, and is assessed as better (△), if live width surpasses 250 relatively, and when a large amount of traces is arranged, then is chosen as poor (*).

These evaluation results are listed in the table 3.

Table 3

	Embodiment							Comparative example
	Embodiment							Comparative example				1	2	3	4	5	6	7	1	2	3	4
	Discharge stability	○	○	○	○	○	○	○	×	×	×	1	2	3	4	5	6	7	1	2	3	4	×
Picture quality	Discharge stability	○	○	○	○	○	○	○	×	×	×	○	○	○	○	○	○	○	×	×	×	×	×

In satisfying embodiment 1～7 ink composite of the relational expression of essential condition of the present invention (1), discharge stability and picture quality are all good.On the other hand, in the ink composite of comparative example 1～4, the difference of dynamic surface tension and static surface tension is greater than 7, and surpassed the scope of formula (1), and it is all poor to discharge stability and picture quality.

As mentioned above, to satisfy relational expression (1), can obtain a kind of ink composite, when it is used for ink-jet recording method, demonstrate good discharge stability, and suppress recording materials and trace occurs by design like this, thereby, the high quality record image is provided.

＜printing ink group 〉

As shown in table 4, the ink composite of embodiment 2～6 and comparative example 1～3 is mixed as cyan, magenta and xanchromatic ink composite, obtain: embodiment printing ink group 1, wherein cyan ink composition contains the C.I. pigment Blue 15: 3 and the C.I. pigment Blue 15: at least a pigment in 4, magenta ink compositions contains at least a C.I of being selected from pigment red 122,209 and the pigment of C.I. pigment violet 19, and the Yellow ink composition contains the pigment of at least a C.I. of being selected from Pigment Yellow 73 74,138,150 and 180; Comparative example printing ink group 1～3, wherein all cyans, magenta and Yellow ink composition all contain the pigment that is different from above-mentioned pigment; And comparative example printing ink group 4, wherein all cyans, magenta and Yellow ink composition contain the pigment that is different from above-mentioned pigment.

Table 4

	Cyan	Magenta	Yellow
	Cyan	Magenta	Yellow	Embodiment printing ink group 1	Embodiment 2 C.I. pigment Blue 15s: 3	Embodiment 4 C.I. pigment red 122s	Embodiment 5 C.I. Pigment Yellow 73s 74
Comparative example printing ink group 1	Comparative example 1 C.I. pigment blue 17	Embodiment 4 C.I. pigment red 122s	Embodiment 6 C.I. Pigment Yellow 73s 180	Embodiment printing ink group 1	Embodiment 2 C.I. pigment Blue 15s: 3	Embodiment 4 C.I. pigment red 122s	Embodiment 5 C.I. Pigment Yellow 73s 74
Comparative example printing ink group 1	Comparative example 1 C.I. pigment blue 17	Embodiment 4 C.I. pigment red 122s	Embodiment 6 C.I. Pigment Yellow 73s 180	Comparative example printing ink group 2	Embodiment 3 C.I. pigment Blue 15s: 4	Comparative example 2 C.I. Pigment reds 58	Embodiment 6 C.I. Pigment Yellow 73s 180
Comparative example printing ink group 3	Embodiment 3 C.I. pigment Blue 15s: 4	Embodiment 4 C.I. pigment red 122s	Comparative example 3 C.I. pigment yellow 13s	Comparative example printing ink group 2	Embodiment 3 C.I. pigment Blue 15s: 4	Comparative example 2 C.I. Pigment reds 58	Embodiment 6 C.I. Pigment Yellow 73s 180
Comparative example printing ink group 3	Embodiment 3 C.I. pigment Blue 15s: 4	Embodiment 4 C.I. pigment red 122s	Comparative example 3 C.I. pigment yellow 13s	Comparative example printing ink group 4	Comparative example 1 C.I. pigment blue 17	Comparative example 2 C.I. Pigment reds 58	Comparative example 3 C.I. pigment yellow 13s

Adopt the embodiment printing ink group 1 of acquisition and each printing ink group of comparative example printing ink group 1～4, on ink-jet recording device, this ink-jet recording device is that commercially available ink-jet recording device (AJ2000: produced by SharpKabushiki Kaisha) obtains through transformation, it with cyan, magenta and Yellow ink composition 1: 1: 1 print over, in satin paper (trade(brand)name: AJ-K4AG) go up printing, thereby form black image.In addition, the ink composite of embodiment 7 is as black ink composition, to obtain identical image.

Measure the image that obtains with spectrophotometer (X-Rite 938: produced by X-Rite Inc.), obtain L ^*a ^*b ^*Brightness index L in the colour system (CIE:1976) ^*With chromaticity index a ^*And b ^*

With following method evaluation test result.In the black image that forms with embodiment 7 ink composites, chromaticity index a ^*And b ^*Get respectively and make A1 and B1, in the black image that forms with embodiment printing ink group 1 and comparative example printing ink group 1～4, chromaticity index a ^*And b ^*Get respectively and make A2 and B2, obtain Δ a by following formula (C) expression ^*b ^*Value, as the evaluation number of black reproducibility:

Δa ^*b ^*＝{(A1-A2) ²+(B1-B2) ²} ^1*2 (C)

Δ a ^*b ^*Value is equal to or less than 20 (Δ a ^*b ^*≤ 20) situation is assessed as (zero), and surpasses 20 (Δ a ^*b ^*＞20) situation is assessed as poor (*).Evaluation result is listed in the table 5.

Table 5

	Evaluation result
	Evaluation result	Embodiment printing ink group 1	○
Comparative example printing ink group 1	×	Embodiment printing ink group 1	○
Comparative example printing ink group 1	×	Comparative example printing ink group 2	×
Comparative example printing ink group 3	×	Comparative example printing ink group 2	×
Comparative example printing ink group 3	×	Comparative example printing ink group 4	×

Table 5 shows, compares with the black image that forms with comparative example printing ink group 1～4, and the black image that forms with embodiment printing ink group 1 has higher density, and this density approaches the black image density with the formation of embodiment 7 ink composites.

As mentioned above, contain the C.I. pigment Blue 15: 3 and the C.I. pigment Blue 15: the cyan ink composition of at least a pigment in 4, contain at least a C.I. of being selected from pigment red 122,209 and the magenta ink compositions of the pigment of C.I. pigment violet 19 and contain the Yellow ink composition of at least a C.I. of being selected from Pigment Yellow 73 74,138,150 and 180 pigment, these 3 kinds of ink composites stacks can be obtained highdensity black image.

The ink composite of the present invention's the 4th embodiment contains at least a tinting material and medium, adopts in the dynamic surface tension that maximum bubble method measures the dynamic surface tension (σ during bubble frequency 10Hz in measuring 24～26 ℃ of temperature ₁₀) and the dynamic surface tension (σ during bubble frequency 1Hz ₁) difference d (σ ₁₀-σ ₁) satisfy following formula (2):

0mN/m≤d≤7mN/m (2)

Maximum bubble method is the capillary method of a kind of mensuration, this method is to insert tubule in liquid, produce bubble by the tubule front end, thereby in liquid, form liquid-gas interface, when the pressure reduction between bubble inside and the outside reaches maximum, promptly when the radius of bubble equals the tubule radius r, measure pressure difference (Δ P), obtain surface tension (σ) from this value then.Surface tension (σ) is obtained by following formula (A).

σ＝ΔP·r/2 (A)

Bubble frequency is the number of bubbles that time per unit produces, and by changing bubble frequency, can obtain the dynamic surface tension from slow mobile status to the quick travel state.By obtaining dynamic surface tension, can estimate the variation of liquid dynamic property from slow mobile status to the quick travel state.

The ink composite of the present embodiment can be on recording materials adopts in the recording method of attaching oil ink composition document image, for example at ink-jet recording method or with employing in the recording method of the handwritten instruments of picture pen and so on etc.Use the ink composite of the present embodiment can stably obtain the high quality record image.

In described recording method, the ink composite of the present embodiment is preferred for ink jet recording method.This ink jet recording method discharges the ink composite drop by exerting pressure to ink composite, and such drop is attached to document image on the recording materials.In ink-jet recording method, use the ink composite of the present embodiment can reach stable discharge, and the high quality record image stably is provided.

In the ink-jet recording device that uses the ink-jet recording method document image, when discharging the ink composite drop continuously, the relief outlet of print cartridge front end from be installed in ink gun, produce the new surface of ink composite incessantly, so the ink composite quick travel is at the quick travel state, when being equivalent to the about 10Hz high frequency of dynamic surface tension, the influence of dynamic surface tension is big.On the other hand, in print cartridge, after ink composite is discharged, ink tank provides ink composite by capillary action, its supply is equivalent to discharge the volume that is reduced, so, ink composite motion slowly, the dynamic surface tension influence during to corresponding with the microinching dynamic surface tension about 1Hz low frequency is greatly.Therefore, because high-frequency dynamic surface tension and low-frequency dynamic surface tension are all exerted one's influence to discharge, so be necessary to consider the balance of high-frequency dynamic surface tension and low-frequency dynamic surface tension, the ink composite drop is stable discharges so that reach.In addition, attached on the recording materials and during document image, ink composite drops on moment quick travel on the recording materials at drop, but slack-off gradually afterwards by the ink composite drop, when recording materials were the absorptivity recording materials, ink composite slowly was penetrated in the recording materials.Promptly; because the dynamic surface tension of ink composite; change into the dynamic surface tension of microinching state from the dynamic surface tension of quick travel state; the difference of high-frequency dynamic surface tension and low-frequency dynamic surface tension strengthens; ink composite extends time of drying on recording materials; thereby cause producing trace or undue infiltration, cause back side ink bleed.

As mentioned above, the ink composite of the present embodiment is designed to, and is using maximum bubble method measuring in the dynamic surface tension of measuring in 24～26 ℃ of the temperature dynamic surface tension (σ during bubble frequency 10Hz ₁₀) dynamic surface tension (σ when the bubble frequency 1Hz ₁) poor d (=σ ₁₀-σ ₁), make and satisfy following formula (2), even the difference of the dynamic surface tension when dynamic surface tension during high frequency 10Hz and low frequency 1Hz within the specific limits, so, in ink-jet recording method, when using the ink composite of the present embodiment, can obtain good discharge stability, can also suppress recording materials and trace occur, thereby the ink composite of high quality document image is provided.

If σ ₁₀With σ ₁Difference d (=σ ₁₀-σ ₁) surpass 7mN/m, the balance variation of the dynamic surface tension when dynamic surface tension during high frequency and low frequency, drop then can not be stablized discharge.And the drying on the recording materials needs the time, and produces trace, thereby makes the picture quality variation.Therefore, select to be equal to or less than 7mN/m.

If σ ₁₀With σ ₁Difference d (=σ ₁₀-σ ₁) less than 0mN/m, the dynamic surface tension during low frequency uprises, ink composite reduces the wettability of the assembly of formation ink gun, and it is difficult that ink composite filling print cartridge becomes.Therefore, select to be equal to or greater than 0mN/m.

Dynamic surface tension (the σ of bubble frequency 10Hz ₁₀) and the dynamic surface tension (σ of bubble frequency 1Hz ₁) preferred 20～70mN/m, more preferably 20～50mN/m.

Work as σ ₁₀And σ ₁During less than 20mN/m, the perviousness of permeating toward the absorptivity recording materials becomes too high, so when adhering on the absorptivity recording materials, ink composite is from drop point zone diffusion towards periphery, the image outline of formation is unintelligible.And work as σ ₁₀And σ ₁When surpassing 70mN/m, the perviousness of permeating toward the absorptivity recording materials became low, and the drying property on the absorptivity recording materials reduces.In addition, the wettability variation of ink composite and print cartridge inwall has hindered ink composite and has been fed in the print cartridge, and ink composite is difficult to be filled to print cartridge, so the ink composite drop can not be stablized discharge.In addition, the new surface of ink composite that is located in the relief outlet of print cartridge front end is difficult to form desirable shape, promptly is difficult to control meniscus, thus ink composite drop continuous high speed ground discharge become impossible.Therefore, the scope of selection is 20～70mN/m.

The ink composite viscosity of the present embodiment preferably is equal to or less than 20mPas in the time of 25 ℃, more preferably be equal to or less than 15mPas.Viscosity surpasses the ink composite of 20mPas in the time of 25 ℃, when being used for ink-jet recording method, and can not stable discharge with the form of ink composite drop.Therefore, the range of viscosities of selection is to be equal to or less than 20mPas.

For medium, can make water or organic solvent etc.

This medium preferably contains water.Thereby can be suppressed on the absorptivity recording materials and trace occurs, and improved drying property.

Preferred 30～95 weight % of water-content in the ink composite, more preferably 30～85 weight %.When water-content during less than 30 weight %, the organic solvent amount is excessive in the ink composite, makes water-soluble or is dispersed in easer stable existence in ink composite in water difficulty that becomes.In addition, the excessive increase of organic solvent component can cause viscosity obviously to increase, and finally can exceed the proper viscosity scope of ink composite.In addition, when water-content surpasses 95 weight %, can excessively reduce the amount of organic solvent, thereby can not keep the wettability of ink composite.Therefore, the scope of its selection is 30～95 weight %.

The specific examples of organic solvent for example, can be enumerated amides, as dimethyl formamide and N,N-DIMETHYLACETAMIDE etc.; Polyalcohols, as polyoxyethylene glycol, polypropylene glycol, ethylene glycol, glycol ether, thiodiglycol, propylene glycol, triglycol, 1,5-pentanediol, 1,4-butyleneglycol, 1,2-hexylene glycol, 1, ammediol, glycerol and 1,2,6-hexanetriol etc.; The ethers of polyvalent alcohol is as gylcol ether, as methyl glycol, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, ethyl carbitol, triglycol monobutyl ether, propylene glycol monoethyl ether, Tetraglycol 99 monomethyl ether and Rokafenol F 1 etc.; Sulfocompound is as tetramethylene sulfone or dimethyl sulfoxide (DMSO) etc.; Nitrogenous compound is as 2-Pyrrolidone, N-Methyl pyrrolidone or ε-Ji Neixianan etc.; Oxygenatedchemicals is as gamma-butyrolactone etc.; The polyfunctional compound, as dimethylaminoethanol, DEAE diethylaminoethanol, trolamine and morpholine etc., but organic solvent is not limited to these examples.These organic solvents can use separately, or two or more mix use.

In these organic solvents, preferred gylcol ether or the polyalcohols of using, because such solvent has low vapour pressure, when containing such solvent in the ink composite, obtained wettability, thereby improve the stability of discharging, so medium preferably contains at least a gylcol ether and polyalcohols.In gylcol ether and polyalcohols, butylcarbitol, propylene glycol monobutyl ether, triglycol monobutyl ether or Tetraglycol 99 monobutyl ether as gylcol ether, perhaps as the glycerol, 1 of polyalcohols, 2-hexylene glycol or 1, the 5-pentanediol because their vapour pressures in the time of 25 ℃ are 0.05 mmhg or lower, and has good wetting action, so adopting them is preferred as medium.

Preferred 3～70 weight % of organic solvent content, more preferably 3～50 weight % in the ink composite.Organic solvent content can cause ink composite rapidly dry during less than 3 weight %, is difficult to keep wettability.And when the content of organic solvent surpassed 70 weight %, water-soluble or water dispersible additive can not stably exist in ink composite.In addition, depend on the kind of used organic solvent, the increase of viscosity is obvious, and exceeds ink composite proper viscosity scope.Therefore, the scope of selection is 3～70 weight %.But, when ink composite contains water as main ingredient, preferred 3～40 weight % of organic solvent content, more preferably 3～30 weight % in the ink composite.Although depend on the kind of using tinting material, when ink composite contains water and surpasses 40 weight % as main ingredient and organic solvent content, can cause the printing quality of resulting records image to descend, prolong the time of drying of ink composite.Therefore, range of choice is 3～40 weight %.

Tinting material can adopt dyestuff, pigment or its mixture.Dyestuff or pigment can be the materials that contains the material of dyestuff or pigment or adhere to dyestuff or pigment thereon.

The generation that can suppress to stop up when in tinting material, using dyestuff, thus the stability of discharging improved.Also can obtain the good document image of photostabilization and water resisting property when in tinting material, adopting pigment.

In order in the color ink-jetting record method, to reappear various colors, used the ink composite of 3 kinds of colors, they are cyan (being abbreviated as C), magenta (being abbreviated as M) and yellow (being abbreviated as Y), the mixing by these ink composites shows various colors.But,, therefore, use black (being abbreviated as B) ink composite to show black usually owing to be difficult to reappear black by 3 kinds of color mixture.The color of the tinting material that contains by change can obtain the ink composite of cyan, magenta, yellow or black.

Dyestuff is had no particular limits, but when ink composite contained water, it was preferred using the water-soluble dye as matching stain, substantive dyestuff, reactive dyestuffs or food dye and so on.In these water-soluble dyes, preferably use water resisting property, photostabilization or security excellent dye.

The specific examples of dyestuff can be enumerated following dyestuff, but dyestuff is not limited to these examples.In following example, represent dyestuff with color index (being called for short C.I.) number.

The dyestuff that can use in cyan ink composition for example, can be enumerated matching stain, as C.I. Acid Blue 7,9,29,45,92 and 249; Substantive dyestuff is as C.I. sun blue 1,2,6,15,22,25,71,76,79,86,90,98,163,165,199 and 202; Reactive dyestuffs are as C.I. Reactive blue 1,2,7,14,15,23,32,38,41,63,80 and 95.In these dyestuffs, preferably use a kind of C.I. of being selected from Acid Blue 7 and 9 and the dyestuff of C.I. sun blue 199 at least.

As the dyestuff that uses in the magenta ink compositions, for example, can enumerate matching stain, as C.I. azogeramine, 8,13,14,18,26,27,35,37,42,52,82,87,89,92,97,106,111,114,115,134,186,249,254 and 289; Substantive dyestuff, directly red 1,4,9,13,17,20,28,31,39,80,81,83,89,225 and 227 as C.I., C.I.

direct orange

26,29,62 and 102; Reactive dyestuffs are as C.I. reactive red 1,14,17,25,26,32,37,44,46,55,58,60,66,74,79,96,97,141,147,180 and 181 etc.In these dyestuffs, preferably use a kind of C.I. of being selected from Xylene Red 52 and 289 and the dyestuff of C.I. reactive red 58,141 and 180 at least.

As the dyestuff that uses in the Yellow ink composition, for example, can enumerate matching stain, as C.I. turmeric yellow 1,7,17,23,42,44,79 and 142; Substantive dyestuff is as C.I. direct yellow 1,12,24,26,33,44,50,86,120,132,142 and 144; Reactive dyestuffs are as C.I. reactive yellow 1,5,11,13,14,20,21,22,25,40,47,51,55,65 and 67.In these dyestuffs, preferably use a kind of C.I. of being selected from turmeric yellow 17 and 23 and direct yellow 86 the dyestuff of C.I. at least.

As the dyestuff that uses in the black ink composition, for example, can enumerate food dye, as C.I. food black 2; Substantive dyestuff directly deceives 19,22,32,38,51,56,71,74,75,77,154,168 and 171 as C.I.; Reactive dyestuffs are as C.I. reactive black 3,4,7,11,12 and 17 etc.In these dyestuffs, preferably use a kind of C.I. edible black 2 and C.I. directly to deceive 154 at least.

Under normal temps, in stable solvable scope, use these dyestuffs.Because every kind of such scope of dyestuff has nothing in common with each other, therefore, dyestuff content is not particularly limited in the ink composite, but preferred 0.1～10 weight %.

As for pigment, can use any in solution dispersible pigment, be preferred but use photostabilization and the good pigment of water resisting property.

The specific examples of pigment comprises following pigment, but pigment is not limited to these examples.In following example, represent with color index (C.I.) number of dyestuff.

As the pigment that uses in the cyan ink composition, for example, can enumerate C.I. pigment blue 1,2,15,16,17,21,22,60 and 64 etc.

As the pigment that uses in the magenta ink compositions, for example, can enumerate C.I.

Pigment red

2,3,5,16,23,31,49,57,63,122 and 209 and C.I. pigment violet 19 etc.

As the pigment that uses in the Yellow ink composition, for example, can enumerate C.I. Pigment Yellow 73 1,2,3,5,12,74,138,150 and 180 etc.

As the pigment that uses in the black ink composition, for example, can enumerate carbon black, for example thermally oxidized black, furnace black, thermal black or dim etc.

In these pigment, the preferred C.I. pigment Blue 15 that uses in cyan ink composition: 3 and the C.I. pigment Blue 15: at least a in 4.For magenta ink compositions, preferably use the pigment of a kind of C.I. of being selected from pigment red 122, C.I Pigment red 209 and C.I. pigment violet 19 at least.And, preferably use the pigment of a kind of C.I. of being selected from Pigment Yellow 73 74, C.I. pigment yellow 13 8, C.I Pigment Yellow 73 150 and C.I. Pigment Yellow 73 180 at least for the Yellow ink composition.For black ink composition, preferably use a kind of above-mentioned sooty pigment that is selected from least.Use these pigment can obtain a kind of ink composite, it can generate the high-quality document image of cyan, magenta, yellow or black.

To use cyan, magenta and the stack of yellow 3 member ink sets compounds of these preferred pigments, promptly adopt the C.I. pigment Blue 15: 3 and the C.I. pigment Blue 15: the cyan ink composition of at least a pigment in 4; Adopt at least a magenta ink compositions that is selected from C.I. pigment red 122, C.I. Pigment red 209 and C.I. pigment violet 19; With at least a Yellow ink composition that is selected from C.I. Pigment Yellow 73 74, C.I. pigment yellow 13 8, C.I. Pigment Yellow 73 150 and C.I. Pigment Yellow 73 180 of employing, can obtain highdensity black recording image, this image approaches the document image with black ink composition formation.That is, the printing ink group that contains above-mentioned 3 kinds of ink composites provides good color balance.Therefore, use contains the printing ink group of these 3 kinds of ink composites, or the printing ink group of 4 kinds of ink composites is these 3 kinds of ink composites and a kind of printing ink group of using the sooty black ink composition, can show various colors, thereby can provide color emissivity good colored document image.

When this ink composite contained water, pigment optimization contained one or more and is selected from for example carboxyl, hydroxyl, amino and sulfonic hydrophilic radical.Such hydrophilic radical can directly be added on the surface of pigments by chemical modification, or is added on the surface of pigments with the polymkeric substance coverage pigment surface of containing such hydrophilic radical, thereby obtains wetting ability.Such hydrophilic radical can also be the form of salt.

But the pigment stable dispersion that contains hydrophilic radical is in aqueous ink composite.Therefore, use the pigment that hydrophilic radical is arranged in tinting material, the generation that can suppress to stop up is not discharged stability and acquisition photostabilization and the good document image of water resisting property thereby do not damage.

But in stable dispersion range, use these pigment at normal temperatures.Because every kind of such scope of dyestuff has nothing in common with each other, so pigment content is not particularly limited in the ink composite, but preferred 0.1～10 weight %.

The ink composite of this embodiment preferably also contains tensio-active agent.Therefore, can be easy to control the dynamic surface tension of ink composite, comprising the dynamic surface tension (σ of bubble frequency 10Hz ₁₀) and the dynamic surface tension (σ of bubble frequency 1Hz ₁).

Tensio-active agent can be non-ionic species tensio-active agent, anionic species tensio-active agent, cationic tensio-active agent or zwitterionics any a kind.Select surfactant types according to the ionogen kind that contains in the ink composite, as nonionic class, cationic and anionic species tensio-active agent.For example, if ink composite contains the anionic property material, then use nonionic class or anionic species tensio-active agent.Such tensio-active agent can mix use.In this case, the kind of tensio-active agent, for example nonionic class, anionic species or cationic tensio-active agent can be identical or different.

In these tensio-active agents, nonionic class tensio-active agent is preferred, because it is not vulnerable to the electrolytical influence that coexists, can make the dynamic surface tension (σ of bubble frequency 10Hz ₁₀) and the dynamic surface tension (σ of bubble frequency 1Hz ₁) difference d (=σ ₁₀-σ ₁) keep within the specific limits, and no matter whether ink composite has added ionogen.

The specific examples of nonionic class tensio-active agent can enumerate with following general formula (IX), (X), (XI), (XII), (XIII) and (XIV) tensio-active agent etc. of expression, but nonionic class tensio-active agent is not subjected to the restriction of these examples.

In general formula (IX), m represents 0～30 integer or mark; N represents 0～30 integer or mark; Integer or mark m and n and (m+n) expression 0～30.

In general formula (X), k represents 11～13 integer or mark; L represents 3～30 integer or mark.

In general formula (XI), h represents 0～11 integer or mark; I represents 0～11 integer or mark; J represents 3～50 integer or mark; Integer or mark h and i and (h+i) expression 9～11.

In general formula (XII), w represents 0～11 integer or mark; X represents 5～9 integer or mark; Y represents 2.5～5 integer or mark; Z represents 0～9 integer or mark; Integer or mark w and z and (w+z) expression 9～11.

In general formula (XIII), p represents 0～78 integer or mark; Q represents 2～15 integer or mark; R represents 0～18 integer or mark.

In general formula (XIV), s represents 0～30 integer or mark; T represents 0～30 integer or mark; But integer or mark s and t and (s+t) expression 0～30.In addition, u represents 0～10 integer or mark; V represents 0～10 integer or mark, but u and v and (u+v) expression 0～10 integer or mark.

In ink composite, preferably contain micelle-forming concentration or be higher than the tensio-active agent of micelle-forming concentration.The surface tension that contains the solution of tensio-active agent is all reducing along with tensio-active agent increases up to micelle-forming concentration, but keeps constant basically on micelle-forming concentration.Therefore, use micelle-forming concentration as mentioned above or be higher than the tensio-active agent of micelle-forming concentration, might make full use of the effect of tensio-active agent, make the dynamic surface tension of the bubble frequency 10Hz that controls by tensio-active agent and the dynamic surface tension of bubble frequency 1Hz keep substantially invariable value, thus the ink composite that acquisition has even performance.

Although the micelle-forming concentration difference of various tensio-active agents, the micelle-forming concentration of any nonionic class tensio-active agent, anionic species tensio-active agent, cationic tensio-active agent and zwitterionics is about 0.001～3 weight % at 25 ℃.

When using pigment in the tinting material, the ink composite of the present embodiment preferably contains resin glue.The existence of resin glue can prevent that pigment from peeling off from recording materials.

As resin glue, can use one or more to be selected from the resin of vibrin, acrylic resin, styrene-propene acid copolymer resin and polyester-acrylic copolymer resin.

Except tinting material, medium, tensio-active agent and resin glue, the ink composite of the present embodiment can further contain other additives, as mould inhibitor, pH value conditioning agent, sequestrant, rust-preventive agent or UV light absorber.

For mould inhibitor, it is preferred using Sodium dehydroacetate, Sodium Benzoate or sodium sorbate etc.

For example, use 0.5～15 weight % tinting material, 3～70 weight % organic solvents, 29～95 weight % water and 0.001～5 weight % tensio-active agent can obtain a kind of ink composite, it contains at least a tinting material and medium, and wherein by maximum bubble method in the dynamic surface tension of 24～26 ℃ of mensuration of temperature, the dynamic surface tension (σ of bubble frequency 10Hz ₁₀) and the dynamic surface tension (σ of bubble frequency 1Hz ₁) satisfy poor the d (=σ of formula (2) ₁₀-σ ₁).

The ink composite of the present invention's the 4th embodiment is used for ink gun 1 shown in Fig. 1～3.Because ink tank 50 has stored the ink composite 60a of above-mentioned the 4th embodiment, such ink composite 60a supplies with print cartridge 40, and discharge with droplet-like from relief outlet 31, so the ink gun 1 of the present embodiment can stably be discharged ink composite 60a drops from relief outlet 31.Such ink gun can realize having the piezoelectric ink jet recording unit of high reliability, and can stablize provides the high quality record image.

The ink composite of the present invention's the 4th embodiment is used for ink gun 2 shown in Fig. 4～6.Identical with the ink gun 1 of the 2nd embodiment, because ink tank 50 has stored the ink composite 60a of the 4th embodiment, and such ink composite 60a supplies with print cartridge 40, and from the form discharge of relief outlet 31 with drop 61a, therefore, the ink gun 2 of the present embodiment can stably be discharged ink composite 60a drop 61a from relief outlet 31.Such ink gun can realize having the hot ink jet type ink-jet recording device of high reliability, and can stablize the high quality document image is provided.

Embodiment

Below will illustrate the present invention in more detail, but the present invention is not subjected to the restriction of these embodiment by embodiment.In these embodiments, image recording is called printing or printing sometimes.

＜ink composite 〉

When the preparation ink composite, as shown in table 6 the kind of tinting material, organic solvent and tensio-active agent and content, and the content of resin glue and water changes, to obtain the ink composite of embodiment 8～14, the wherein dynamic surface tension (σ of bubble frequency 10Hz ₁₀) and the dynamic surface tension (σ of bubble frequency 1Hz ₁) have a poor d (=σ that satisfies formula (2) ₁₀-σ ₁), and the ink composite of comparative example 5～8, wherein d does not satisfy formula (2).In table 6, the unit of each hurdle value represents that with weight part each ink composite total amount of embodiment 8～14 and comparative example 5～8 is respectively 100 weight parts.In addition, in table 6, TEGBE represents the triglycol monobutyl ether; PEG400 represents the polyoxyethylene glycol of molecular weight 400; The tensio-active agent that general formula (IX) expression is represented with general formula (IX); The tensio-active agent that general formula (X) expression is represented with general formula (X); The tensio-active agent that general formula (XI) expression is represented with general formula (XI); The tensio-active agent that general formula (XII) expression is represented with general formula (XII); The tensio-active agent that general formula (XIII) expression is represented with general formula (XIII); The tensio-active agent that 1 expression of fluorine class tensio-active agent is represented with chemical formula (XV); The tensio-active agent that 2 expressions of fluorine class tensio-active agent are represented with chemical formula (XVI).Surfactant concentration is equal to or higher than micelle-forming concentration in embodiment 8～14 and the comparative example 5～7 in the ink composite, but less than the micelle-forming concentration of comparative example 8.

When bubble frequency 0.5～35Hz, measure the dynamic surface tension of embodiment 8～14 and comparative example 5～8 with tensiometer (BP-4: produce) by Kyowa KaimenKagaku Co..

Table 7 illustrates the dynamic surface tension (σ of the ink composite of embodiment 8～14 and comparative example 5～8 at bubble frequency 10Hz ₁₀) and at the dynamic surface tension (σ of bubble frequency 1Hz ₁) difference d (mN/m) (=σ ₁₀-σ ₁) and mensuration temperature at this moment (℃).

Table 6

Composition			Embodiment							Comparative example
			Embodiment							Comparative example				8	9	10	11	12	13	14	5	6	7	8
				Dyestuff	C.I. sun blue 199	2.5								8	9	10	11	12	13	14	5	6	7	8
	C.I. pigment Blue 15: 3			Dyestuff	C.I. sun blue 199	2.5								3
	C.I. pigment Blue 15: 3			C.I. pigment Blue 15: 4			3							3
	C.I. pigment red 122			C.I. pigment Blue 15: 4			3									5
	C.I. pigment red 122			C.I. Pigment Yellow 73 74					4							5
	C.I. Pigment Yellow 73 180			C.I. Pigment Yellow 73 74					4									4
	C.I. Pigment Yellow 73 180			Carbon black							5							4							5
	C.I. pigment blue 17			Carbon black							5									2					5
	C.I. pigment blue 17			C.I. Pigment red 58									3							2
	C.I. pigment yellow 13			C.I. Pigment red 58									3									2
	C.I. pigment yellow 13					Glycol ether	8	8	8	5	5	8	8									2		2	5	20	10
Glycerol	5	7	8			Glycol ether	8	8	8	5	5	8	8	10	8	8	9	5	5	17	10			2	5	20	10
Glycerol	5	7	8			1, the 5-pentanediol			2	5	2	2	5	10	8	8	9	5	5	17	10		2	18	5
TEGBE	8	8	8			1, the 5-pentanediol			2	5	2	2	5	5	5	3	6	4			8		2	18	5
TEGBE	8	8	8			PEG400		1						5	5	3	6	4			8	10	15	15	10
		General formula (IX) (m+n=10)				PEG400		1						1	1							10	15	15	10
		General formula (IX) (m+n=10)		General formula (X) (k=11～13,1=15)			1				1.0			1	1								0.001
		General formula (XI) (h+i=9～11, j=9)		General formula (X) (k=11～13,1=15)			1				1.0					1.5							0.001
		General formula (XI) (h+i=9～11, j=9)		General formula (XII) (w+z=9～11, x=9, y=5)					1.5							1.5
		General formula (XIII) (p=12, q=8, r=4)		General formula (XII) (w+z=9～11, x=9, y=5)					1.5									1
		General formula (XIII) (p=12, q=8, r=4)		Fluorine class tensio-active agent 1								1						1
		Fluorine class tensio-active agent 2		Fluorine class tensio-active agent 1								1									1.5			1
		Fluorine class tensio-active agent 2		Resin glue		Vibrin	Do not have	1	1.5	2	1	1.5	1								1.5	1	1.5	1		2	2
Water			R	Resin glue		Vibrin	Do not have	1	1.5	2	1	1.5	1	R	R	R	R	R	R	R	R	1	1.5	R	R	2	2

R: surplus

Table 7

	Dynamic surface tension σ at 10Hz ₁₀(mN/m)	Dynamic surface tension σ at 1Hz ₁(mN/m)	d(mN/m)	The mensuration temperature (℃)
	Dynamic surface tension σ at 10Hz ₁₀(mN/m)	Dynamic surface tension σ at 1Hz ₁(mN/m)	d(mN/m)	The mensuration temperature (℃)	Embodiment 8	31.9	26.7	5.2	25.3～25.7
Embodiment 9	31.9	26.7	5.2	25.2～25.6	Embodiment 8	31.9	26.7	5.2	25.3～25.7
Embodiment 9	31.9	26.7	5.2	25.2～25.6	Embodiment 10	34.5	29.5	5	24.9～25.3
Embodiment 11	34.7	29.6	5.1	24.7～25.2	Embodiment 10	34.5	29.5	5	24.9～25.3
Embodiment 11	34.7	29.6	5.1	24.7～25.2	Embodiment 12	34.4	29.1	5.3	24.8～25.2
Embodiment 13	34.8	29.7	5.1	25.0～25.4	Embodiment 12	34.4	29.1	5.3	24.8～25.2
Embodiment 13	34.8	29.7	5.1	25.0～25.4	Embodiment 14	34.6	29.5	5.1	25.3～25.7
Comparative example 5	31.4	24.3	7.1	25.1～25.6	Embodiment 14	34.6	29.5	5.1	25.3～25.7
Comparative example 5	31.4	24.3	7.1	25.1～25.6	Comparative example 6	29.5	22.0	7.5	25.1～25.6
Comparative example 7	29.5	22.2	7.3	25.0～25.5	Comparative example 6	29.5	22.0	7.5	25.1～25.6
Comparative example 7	29.5	22.2	7.3	25.0～25.5	Comparative example 8	38.9	25.5	13.4	24.8～25.2

Estimate the picture quality of the stable and resultant document image of embodiment that obtains 8～14 of institute and comparative example 5～8 ink composites discharge when being used for ink jet recording method in the following manner.

＜discharge stable 〉

The ink composite of embodiment 8～14 that obtains and comparative example 5～8 is filled to respectively in the ink tank of ink-jet recording device, this ink-jet recording device is that commercially available ink-jet recording device (AJ2000: produced by SharpKabushiki Kaisha) obtains through transformation, so that ink gun 1 as shown in Figure 1 can be installed, with the print speed of 7 pages of A4 paper per minutes, with the print density 5% continuous plain copying paper of producing at Sharp KabushikiKaisha (trade(brand)name: SF4AM3) go up printing.In this test, when the ink tank sky time recharge ink composite, print continuously up to can not discharge from nozzle because of the ink composite drop can not print again till, counting is up to the paper quantity of printing fully at the moment, obtain printable paper number, as estimating the index of discharging stability.If printable paper number surpasses 200, be assessed as (zero), if quantity is 150～200, be assessed as better (△), if be less than 150, be assessed as poor (*).

＜picture quality 〉

In addition, the ink composite of embodiment 8～14 that obtains and comparative example 5～8 is filled to respectively in the ink tank of ink-jet recording device, this ink-jet recording device is that commercially available ink-jet recording device (AJ2000: produced by Sharp Kabushiki Kaisha) obtains through transformation, so that ink gun 1 shown in Figure 1 can be installed, plain copying paper (trade(brand)name: SF4AM3) go up the specific pattern of printing, in Sharp Kabushiki Kaisha production with the image that obtains to be used to estimate.The image of estimating was placed one day, and pattern line-width is set at 100, measures the pattern line-width relative value of each evaluation map picture, as the index of assess image quality.If relative live width is less than 150 and almost do not have trace, the result just is chosen as (zero); If live width is 150～250 relatively, some traces are arranged, be assessed as better (△); If live width surpasses 250 relatively, and abundant traces is arranged, then be chosen as poor (*).

Above evaluation result is listed in the table 8.

Table 8

	Embodiment							Comparative example
	Embodiment							Comparative example				8	9	10	11	12	13	14	5	6	7	8
	Discharge stability	○	○	○	○	○	○	○	×	×	×	8	9	10	11	12	13	14	5	6	7	8	△
Picture quality	Discharge stability	○	○	○	○	○	○	○	×	×	×	○	○	○	○	○	○	○	×	×	×	×	△

In the ink composite of embodiment 8～14, the dynamic surface tension (σ of bubble frequency 10Hz wherein ₁₀) with the dynamic surface tension (σ of bubble frequency 1Hz ₁) difference d (=σ ₁₀-σ ₁) satisfying formula (2), its discharge stability and picture quality are all good.On the other hand, in the ink composite of comparative example 5～8, their poor d is greater than 7, and surpassed the scope of formula (2), discharges stability and picture quality and is difference or better.

As mentioned above, so design the dynamic surface tension (σ that makes bubble frequency 10Hz ₁₀) with the dynamic surface tension (σ of bubble frequency 1Hz ₁) difference d (=σ ₁₀-σ ₁) satisfy formula (2), might obtain a kind of ink composite that is used for ink jet recording method, said composition demonstrates good discharge stability, and suppresses trace to occur on the recording materials, and the high quality document image is provided.

＜printing ink group 〉

As shown in table 9, the ink composite of embodiment 9～13 and comparative example 5～7 is mixed as cyan, magenta and xanchromatic ink composite, to obtain containing the C.I. pigment Blue 15: 3 and the C.I. pigment Blue 15: the cyan ink composition of at least a pigment in 4, contain at least a C.I. of being selected from pigment red 122,209 and the magenta ink compositions of C.I. pigment violet 19 pigment, contain the Yellow ink composition of at least a C.I. of being selected from Pigment Yellow 73 74,138,150 and 180 pigment and constitute embodiment printing ink group 2; Make comparative example printing ink group 5～7, wherein any pigment in cyan, magenta and the Yellow ink composition is different from above-mentioned pigment; Make comparative example printing ink group 8, the pigment that wherein all cyans, magenta and Yellow ink composition contain is different from above-mentioned pigment.

Table 9

	Cyan	Magenta	Yellow
	Cyan	Magenta	Yellow	Embodiment printing ink group 2	Embodiment 9 C.I. pigment Blue 15s: 3	Embodiment 11 C.I. pigment red 122s	Embodiment	12 C.I. Pigment Yellow 73s 74
Comparative example printing ink group 5	Comparative example 5 C.I. pigment blue 1s 7	Embodiment 11 C.I. pigment red 122s	Embodiment	Embodiment printing ink group 2	Embodiment 9 C.I. pigment Blue 15s: 3	Embodiment 11 C.I. pigment red 122s	Embodiment	12 C.I. Pigment Yellow 73s 74	13 C.I. Pigment Yellow 73s 180
Comparative example printing ink group 5	Comparative example 5 C.I. pigment blue 1s 7	Embodiment 11 C.I. pigment red 122s	Embodiment	Comparative example printing ink group 6	Embodiment 10 C.I. pigment Blue 15s: 4	Comparative example 6 C.I. Pigment reds 58	Embodiment 13 C.I. Pigment Yellow 73s 180		13 C.I. Pigment Yellow 73s 180
Comparative example printing ink group 7	Embodiment 10 C.I. pigment Blue 15s: 4	Embodiment 11 C.I. pigment red 122s	Comparative example 7 C.I. pigment yellow 13s	Comparative example printing ink group 6	Embodiment 10 C.I. pigment Blue 15s: 4	Comparative example 6 C.I. Pigment reds 58	Embodiment 13 C.I. Pigment Yellow 73s 180
Comparative example printing ink group 7	Embodiment 10 C.I. pigment Blue 15s: 4	Embodiment 11 C.I. pigment red 122s	Comparative example 7 C.I. pigment yellow 13s	Comparative example printing ink group 8	Comparative example 5 C.I. pigment blue 1s 7	Comparative example 6 C.I. Pigment reds 58	Comparative example 7 C.I. pigment yellow 13s

Adopt resulting embodiment printing ink group 2 and comparative example printing ink group 5～8 respectively, and use ink-jet recording device, this ink-jet recording device is that commercially available ink-jet recording device (AJ2000: produced by Sharp KabushikiKaisha) obtains through transformation, with cyan, magenta and 1: 1: 1 printing ratio of Yellow ink composition, in satin paper (trade(brand)name: AJ-K4AG) go up printing, thereby form black image.In addition, use the ink composite of embodiment 14 as black ink composition, to obtain identical image.

Measure each resulting black image with spectrophotometer (X-Rite 938: produced by X-Rite Inc.), obtain L ^*a ^*b ^*Brightness index L in the colour system (CIE:1976) ^*With chromaticity index a ^*, b ^*

Evaluation test result as follows.In the black image that forms with embodiment 14 ink composites, chromaticity index a ^*And b ^*Get respectively and make A1 and B1, in the black image that forms with embodiment printing ink group 2 and comparative example printing ink group 5～8, chromaticity index a ^*And b ^*Get respectively and make A2 and B2, obtain Δ a with following formula (C) expression ^*b ^*Value, as the evaluation index of black reproducibility:

Δa ^*b ^*＝{(A1-A2) ²+(B1-B2) ²} ^1/2 (C)

Δ a ^*b ^*Value is equal to or less than 20 (Δ a ^*b ^*≤ 20) situation is assessed as (zero), and surpasses 20 (Δ a ^*b ^*＞20) situation is assessed as poor (*).Evaluation result is listed in the table 10.

Table 10

	Evaluation result
	Evaluation result	Embodiment printing ink group 2	○
Comparative example printing ink group 5	×	Embodiment printing ink group 2	○
Comparative example printing ink group 5	×	Comparative example printing ink group 6	×
Comparative example printing ink group 7	×	Comparative example printing ink group 6	×
Comparative example printing ink group 7	×	Comparative example printing ink group 8	×

Table 10 shows, compare with 3 kinds of ink composite stack black images that form that contain respectively in the comparative example printing ink group 5～8,3 kinds of ink composites that contain in the embodiment printing ink group 2 formed black image that superposes has more high-density, and this density approaches the density with the formed black image of embodiment 14 ink composites.Therefore, can conclude that compare with comparative example printing ink group 5～8, embodiment printing ink group 2 has better black reproducibility and good color balance.

As mentioned above, containing the C.I pigment Blue 15: 3 and the C.I pigment Blue 15: the cyan ink composition of at least a pigment in 4, contain at least a C.I. of being selected from pigment red 122,209 and the magenta ink compositions of C.I. pigment violet 19 pigment and the Yellow ink composition that contains at least a C.I. of being selected from Pigment Yellow 73 74,138,150 and 180 pigment superposeed, can obtain having the printing ink group of good color balance.

Under the prerequisite that does not break away from spirit of the present invention or essential characteristic, available other variety of ways are specifically implemented.Therefore, can think that these schemes all are illustrative and not restrictive in all fields, scope of the present invention is by claims rather than indicated by above-mentioned specification sheets, and therefore, all changes that belong in claims scope all are included in the scope of the invention.

Claims

1. an ink composite contains a kind of tinting material, medium and tensio-active agent at least, wherein,

Adopt down in the dynamic surface tension of maximum bubble method mensuration 24～26 ℃ of temperature, bubble frequency is the dynamic surface tension (σ of 10Hz ₁₀) with bubble frequency be the dynamic surface tension (σ of 1Hz ₁) difference d (=σ ₁₀-σ ₁) satisfy following formula (2):

0mN/m≤d≤7mN/m (2)

2. ink composite according to claim 1, wherein, bubble frequency is the dynamic surface tension (σ of 10Hz ₁₀) with bubble frequency be the dynamic surface tension (σ of 1Hz ₁) scope be 20～70mN/m.

3. ink composite according to claim 1, wherein, medium contains water.

4. ink composite according to claim 1, wherein, medium contains at least a in gylcol ether or the polyalcohols.

5. ink composite according to claim 1, wherein, tinting material comprises dyestuff.

6. ink composite according to claim 1, wherein, tinting material comprises pigment.

7. ink composite according to claim 3, wherein, tinting material comprises the pigment with hydrophilic radical.

8. ink composite according to claim 1, wherein, tensio-active agent comprises nonionic class tensio-active agent.

9. ink composite according to claim 1 wherein, contains the tensio-active agent that is equal to or higher than micelle-forming concentration.

10. ink composite according to claim 6, wherein, described pigment comprises the C.I pigment Blue 15: 3 or the C.I. pigment Blue 15: 4 at least a.

11. ink composite according to claim 6, wherein, pigment comprises the pigment of at least a C.I. of being selected from pigment red 122, C.I Pigment red 209 and C.I. pigment violet 19.

12. ink composite according to claim 6, wherein, pigment comprises the pigment of at least a C.I of being selected from Pigment Yellow 73 74, C.I pigment yellow 13 8, C.I Pigment Yellow 73 150 and C.I. Pigment Yellow 73 180.

13. ink composite according to claim 6, wherein, described pigment comprises carbon black.

14. an image recording process comprises:

With ink composite attached on the recording materials,

Wherein ink composite uses the described ink composite of claim 1.

15. an image recording process comprises:

To the ink composite pressurization, the ink composite drop is discharged; And

With drop attached on the recording materials,

Wherein ink composite uses the described ink composite of claim 1.

16. recording method according to claim 14 wherein, for ink composite, is used the described ink composite of claim 10, the described ink composite of claim 11 and the described ink composite of claim 12 at least.

17. recording method according to claim 15 wherein, for ink composite, is used the described ink composite of claim 10, the described ink composite of claim 11 and the described ink composite of claim 12 at least.

18. recording method according to claim 14, wherein, for ink composite, use the described ink composite of claim 10, the described ink composite of claim 11, the described ink composite of claim 12 and the described ink composite of claim 13 at least.

19. recording method according to claim 15, wherein, for ink composite, use the described ink composite of claim 10, the described ink composite of claim 11, the described ink composite of claim 12 and the described ink composite of claim 13 at least.

20. a document image, this image are to adopt the described recording method record of claim 14.

21. a document image, this image are to adopt the described recording method record of claim 15.

22. a printing ink group contains:

The described ink composite of claim 10;

The described ink composite of claim 11; With

The described ink composite of claim 12.

23. a printing ink group contains:

The described ink composite of claim 10;

The described ink composite of claim 11;

The described ink composite of claim 12 and

The described ink composite of claim 13.

24. an ink gun comprises:

Store the ink tank of the described ink composite of claim 1;

Print cartridge, it has one to be used to discharge the relief outlet of ink composite drop and to receive ink composite from ink tank;

Produce deformation and be provided in piezoelectric element to the small part print cartridge with applying voltage, be used for the contained ink composite of print cartridge is exerted pressure; With

Apply the electrode of voltage to piezoelectric element.

25. an ink gun comprises:

Store the ink tank of the described ink composite of claim 1;

Print cartridge, it has one to be used to discharge the relief outlet of ink composite drop and to receive ink composite feed from ink tank;

At the Heating element that is equipped with to the small part print cartridge, this element is used for heating the contained ink composite of print cartridge, makes it produce bubble, thereby exerts pressure to ink composite; With

Apply the electrode of voltage to Heating element.

26. a document image, this image are attached to the enterprising line item of recording materials by ink composite drop that the described ink gun of claim 24 is discharged.

27. a document image, this image are attached to the enterprising line item of recording materials by ink composite drop that the described ink gun of claim 25 is discharged.