CN101426657A

CN101426657A - Ink media set, ink composition, ink cartridge, inkjet recording method, inkjet recording apparatus, and ink recorded matter

Info

Publication number: CN101426657A
Application number: CNA2007800138452A
Authority: CN
Inventors: 松山彰彦; 有贺保; 诸星直哉; 大嶋亨; 后藤宽
Original assignee: Ricoh Co Ltd
Current assignee: Ricoh Co Ltd
Priority date: 2006-12-27
Filing date: 2007-12-26
Publication date: 2009-05-06
Anticipated expiration: 2027-12-26
Also published as: JP4971784B2; CN101426657B; JP2008162097A

Abstract

An ink-media set, comprising an ink composition and a recording medium, wherein the ink composition comprises a polymer fine particle containing a dye and an inorganic pigment particle, a water-soluble solvent, and water, and has a surface tension of 20 mN/m to 35 mN/m at 25 DEG C, and the recording medium comprises a support and a coating layer on at least one side of the support, and the amount of pure water transferred to the recording medium is no less than 2 ml/m2 and less than 35 ml/m2 at a contact period of 100 ms and the amount of pure water transferred to the recording medium is no less than 3 ml/m2 and less than 40 ml/m2 at a contact period of 400 ms by measurement of a dynamic scanning absorptometer.

Description

Printing ink-media pack, ink composite, print cartridge, ink jet recording method, ink-jet recording apparatus and ink recorded matter

Technical field

Even the present invention relates to also to provide printing ink-media pack and the ink composite that has than the high quality image of high color saturation and enough tones on the recording medium of low absorbency, also relate to the ink jet recording method, ink-jet recording apparatus and the ink recorded matter that utilize this printing ink-media pack.

Background technology

Ink-jet printer relies on its low environment noise and low operating cost, catches on undoubtedly, and can obviously popularize in market at the color printer that prints on the plain paper.Yet, it is difficult to satisfy, and the colorrendering quality, wearability, light resistance, gasproof, resistance to water, the drying property of image, the character that comprise image spread the diffusion (bleeding) at (spreading) (emergence (feathering)), color boundaries place, the density unevenness of part is spared all necessary performances of property (Cheng Zhu (beading)), printed on both sides ability and jetting stability on the spot, thereby ink composite and recording medium are selected according to the preferential performance of several applications.

The ink composite that is used for ink mist recording is typically based on the wetting agent that is mixed with colouring agent and is used to prevent stop up such as the water of glycerine.Described colouring agent is mainly can know painted water-soluble dye.

Yet because light resistance, gasproof and poor water resistance, dyestuff has obsolete inferior problem on plain paper.For addressing this problem, used ink-jet specific record paper, and attempted to improve these tolerances, but still had the problem of quality deficiency with ink absorbing layer.

Therefore in recent years, can provide the viewpoint of excellent light resistance, gasproof and resistance to water, adopt pigment based on pigment.Yet, to compare with dyestuff, pigment has the relatively poor problem of coloring.Its reason is considered to have the light of different wave length and phase place because the multipath reflection of light and interfering in pigment.

Therefore, when pigment is used for the colouring agent of composition for ink jet recording, the problem that for example color saturation descends and glossiness descends in ink jet recording paper in common paper has appearred.In order to address these problems, to attempt by making the meticulousr color saturation that improves of granules of pigments, or attempt to improve glossiness by coated polymer on granules of pigments; Yet, aspect coloring, still there are differences with dyestuff.

In addition, the paper of employing high-hydroscopicity such as common paper and ink-jet specific record paper are as the ink mist recording recording medium; This paper is measured by the dynamic scan absorptiometer, and typical earth surface reveals at 100ms and is higher than 35ml/m time of contact ²Be higher than 40ml/m time of contact at 400ms ²The pure water transfer amount to recording medium.

Common paper with high-hydroscopicity like this is because thin and cheap but favourable, but because of the colouring component of ink composite is easy to infiltrate in the paper, causes the quantitative change of colouring component on the surface little, thereby have image coloring difference and the dark problem of impression.The absorbability of ink-jet specific record paper can provide by the layer that inorganic pigment or water absorbent polymer are set from the teeth outwards, thereby colouring component can be retained in around the surface, and can cause high coloring; Yet ink-jet specific record paper is compared with common paper, has the big and cost problem of higher of thickness.

And, can exemplify on its surface and do not have the polymer film of receiving layer as recording medium.Described polymer film is measured by the dynamic scan absorptiometer, and typical earth surface reveals at 100ms and is lower than 2ml/m time of contact ²Be lower than 3ml/m time of contact at 400ms ²The pure water transfer amount to recording medium.

Polymer film as recording medium absorbs water hardly, thereby because promoters (spur) (hereinafter being called " promoters stain (spur stain) " sometimes), Cheng Zhu and the back pollution when piling up, often produce that for example anti-seal pollutes and the problem of printing ink disappearance, cause this polymer film far can not practicality thus.

And, can exemplify surface-coated paper as recording medium.This surface-coated paper is measured by the dynamic scan absorptiometer, and typical earth surface reveals 2-35ml/m time of contact at 100ms ²With at 400ms 3-40ml/m time of contact ²The pure water transfer amount to recording medium.This surface-coated paper is as being mainly used in the recording medium that for example lithographic printing and intaglio printing are used, and has lower thickness and little with the common paper difference in price.When on recording medium, adopting colouring agent to be the aqueous ink-jet inks formation image of pigment,, therefore can obtain to have the high quality image of excellent coloring and high gloss because colouring agent keeps from the teeth outwards.Yet, when colouring agent is water soluble dyestuffs, there is the low and dark problem of color density obtain, because migrating in the base material (cellulose) with moisture and aqueous solvent, the hole of colouring agent by coating on the surface keep from the teeth outwards.

And, when adopting pigment ink, can obtain high rendered image, but because the slow drying of ink composite, produced for example promoters stain, Cheng Zhu and the problem of back pollution when piling up.

For solving the drying of ink composite, several different methods has been proposed.For example, proposed to use the method (referring to patent documentation 1) of strong basicity printing ink.Yet this proposal for example exists that the fixation performance of operational hazards, acid-free paper is tending towards obvious decline, be easy to print through and obviously be difficult to the problem of double-sided recording modes.

Also proposed to use and contained the recording method based on the ink composite of oil of water-insoluble organic solvent as liquid medium.Yet although the fixation performance excellence, because the security of handling organic solvent and the measure of smell must be arranged, so this proposal only limits to commercial Application, is unsuitable for adopting in office and general home environment.

Proposed a kind of method that adopts ink composite, wherein said ink composite comprises the exhibiting high surface activating agent or has surfactant (referring to patent documentation 2) than low surface tension.The ink composite of this proposal is compared with conventional ink composite, shows excellent rate of drying after the printing, yet hand can be made dirty according to the kind of paper when picking up printed matter on the tape deck with hand immediately, or tangible emergence can occur according to paper type.

Also proposed a kind of recording method, be down the ink composite heating of waxy solid wherein, and under molten condition, spray with record (referring to patent documentation 3) with normal temperature.Yet this proposal has caused the bossing of print character, and when a large amount of printed matters piled up and place, this had produced for example print character transfer and/or the coherent problem of paper.In addition, need heating unit to heat this ink composite, this makes device complicated.

Also proposed a kind of dry method that promotes, wherein behind print character, record-paper has been heated (referring to patent documentation 4).Yet there is the problem of big power consumption in this proposal owing to need warm-up mill and warm-air drier, makes it to be difficult to use in office or general family.

As mentioned above, compare, show the coloring of excellence based on the colouring agent of dyestuff, but, when combining, show unacceptable quality with common paper as mentioned above owing to light resistance, gasproof and poor water resistance with colouring agent based on pigment.

Be to solve the problem of light resistance, gasproof and resistance to water, proposed to use the method for colouring agent,, form colouring agent (referring to patent documentation 5-8) wherein with the dyestuff dissolving or be included in the polymer particles.In these were proposed, dyestuff was water-fast basically, and its resistance to water and gasproof and pigment are suitable, and keep high dye coloring.Yet these proposals only limit to record on common paper or ink-jet specific record paper, when having on the low absorbefacient recording medium, particularly are lower than 4ml/m in the pure water amount that shifts to recording medium time of contact in 100ms ²Be lower than 5ml/m time of contact at 400ms ²Recording medium on when writing down, produce the problem that for example becomes pearl and drying property deficiency.

Being applied to based on the colouring agent of dyestuff under the situation with low absorbefacient recording medium, for solving the drying property problem, also proposed dyestuff is included in the polymer emulsion, and improved aqueous ink composition method of viscosity (referring to patent documentation 9).Because viscosity higher has caused the higher solid content of ink composite and drier, therefore this proposal may be effectively for the record-paper with high absorbance, but exists not enough for having low absorbefacient recording medium.

Therefore, need at present a kind of printing ink-media pack of exploitation, it and also can provide the high quality image that has than high color saturation and enough tones having not only on common paper and ink-jet specific record paper on the recording medium of low absorbency.

Ink mist recording shows the higher absorbency similar with ink-jet specific record paper to common paper with recording medium, and corresponding to measuring by the dynamic scan absorptiometer, the pure water amount that in recording medium, shifts 100ms in time of contact usually above 15ml/m ²And be higher than 20ml/m in time of contact at 400ms ²Those.It is advantageously thin and cheap to have this enough absorbefacient common paper, yet, produced for example problem of print through in the paper because the colouring component of printing ink is tending towards infiltrating, and because the quantitative change of lip-deep colouring component is few, coloring difference and image cause dim impression.On the other hand, specific record paper has absorbability by the layer that inorganic pigment or water absorbent polymer are set from the teeth outwards, thereby colouring component can be retained in around the surface, and can cause high coloring; Yet, to compare with common paper, there is the big and cost problem of higher of thickness in ink-jet specific record paper.

On the contrary, for measuring by the dynamic scan absorptiometer, the amount of the ink composite that shifts to recording medium is lower than 4ml/m at 100ms in time of contact ²Be lower than 7ml/m at 400ms in time of contact ²The recording medium that shows low absorbency, can exemplify do not have receiving layer on its surface polymer film as this recording medium.Polymer film as described recording medium absorbs printing ink hardly, thereby for example often produces because of promoters, Cheng Zhu and back pollution causes when piling up anti-seal pollutes and the problem of printing ink disappearance, thereby this polymer film far can not be practical.

For measuring by the dynamic scan absorptiometer in the aforementioned recording medium, the amount of the ink composite that shifts to recording medium is 4-15ml/m in 100ms time of contact ²And in 400ms time of contact is 7-20ml/m ²The recording medium with medium absorbency, can exemplify and be mainly used in for example surface-coated paper of lithographic printing and intaglio printing.These recording mediums are thin, and price and common paper difference are little.Because ink setting is slow in these recording mediums, in these recording mediums, exists and promoters stain, Cheng Zhu for example take place and the problem of back pollution when piling up.

When adopting aqueous ink-jet inks on these recording mediums, to form image, because colouring agent under the dissolved state such as water-soluble dye migrate in the base material (cellulose) with moisture and aqueous solvent by the hole of surface coating, and do not keep from the teeth outwards, therefore produced for example high oozing out and print through, low-density and painted dark problem.

When colouring agent shows as the dispersing of pigments state, because colouring agent keeps from the teeth outwards, therefore to compare with water-soluble dye, coloring may be excellent; Yet, can not cause the not satisfied image of coloring from essence the coloring of difference being improved to the level of pigment.

On the other hand; when under dispersity, using water-insoluble dyestuff such as oil-soluble dyes and disperse dyes; because colouring agent can be retained in the surface; therefore can often obtain painted clearly, thereby water-insoluble dyestuff is considered to very suitable for having low absorbefacient recording medium.Yet this water-insoluble dye soluble is separated the organic solvent in printing ink, thereby water-insoluble dyestuff is partly dissolved in the ink carrier, and the dyestuff of dissolved state causes the intrinsic color of dyestuff painted clearly.Therefore, when the meltage of dyestuff is too much, has produced and be similar to for example oozing out and print through, low-density and painted dark problem of water-soluble dye.

For the method for the problem that solves above-mentioned drying property aspect, proposed to use and contained the recording method based on the ink composite of oil of water-insoluble organic solvent as liquid medium; Yet although the fixation performance excellence, because the security of handling organic solvent and the measure of smell must be arranged, so this proposal only limits to commercial Application, is unsuitable for adopting in office and general home environment.

Be to improve light resistance, gasproof and the resistance to water of dyestuff, patent documentation 5-8 has proposed the dyestuff dissolving or has been included in colouring agent in the polymer particles.Patent documentation 10 has proposed further interpolation inorganic pigment.These proposals can make that resistance to water and gasproof and pigment are suitable, but its application is limited to record on common paper and ink-jet specific record paper, can not solve for example Cheng Zhu when implementing record on being similar to low absorbability recording medium of the present invention and the problem of drying property.

Patent documentation 11 has proposed pigment ink or the colored polymeric particulate ink printing that covers dyestuff with polymer are being similar on low absorbability recording medium of the present invention such as art paper and the printing paper.Yet the printing ink that colouring agent wherein is insoluble to ink carrier substantially and disperses with graininess is paid close attention in this invention, does not improve coloring and do not relate to as of the present invention by being partly dissolved colouring agent.

Patent documentation 1: Japanese Patent Application Laid-Open (JP-A) 63-2996

Patent documentation 2:JP-A 60-34992

Patent documentation 3:JP-A 02-18710

Patent documentation 4:JP-A 2003-72059

Patent documentation 5: Japan Patent (JP-B) 3821306

Patent documentation 6:JP-B 3817813

Patent documentation 7:JP-B 3839894

Patent documentation 8:JP-B 2977817

Patent documentation 9:JP-A 2005-306899

Patent documentation 10:JP-A 2006-307165

Patent documentation 11:JP-A 2006-206666

Summary of the invention

The situation that the present invention is based on prior art is made, and purpose is to address the above problem and reaches following purpose.Promptly, it is a kind of not only on common paper or ink-jet specific record paper that the object of the invention is to provide, even also can form printing ink-media pack and the ink composite that has than the high quality image of high color saturation and enough tones on the recording medium of low absorbency having, the ink jet recording method, ink-jet recording apparatus and the ink recorded matter that use described printing ink-media pack also are provided.

The inventor furthers investigate for addressing the above problem, and obtains following the discovery.That is, described being found to be the combination of specific ink composition and specific recording medium not only on common paper or ink-jet specific record paper, even also can form the high quality image that has than high color saturation and enough tones having on the recording medium of low absorbency.

The present invention is based on the inventor's above-mentioned discovery, and the problems referred to above can be solved by the present invention as follows:

＜1〉a kind of printing ink-media pack comprises ink composite and recording medium,

Wherein ink composite comprises polymer particles, water-soluble solvent, the He Shui that contains dyestuff and inorganic pigment granules, and has the surface tension of 20mN/m-35mN/m under 25 ℃, and

Recording medium comprises support and in this support coating on the one side at least, measures by the dynamic scan absorptiometer, and the pure water amount that shifts to this recording medium is not less than 2ml/m time of contact at 100ms ²And less than 35ml/m ², be not less than 3ml/m time of contact at 400ms ²And less than 40ml/m ²

＜2〉according to＜1〉printing ink-media pack, wherein the viscosity of ink composite is 5mPas to 50mPas down at 25 ℃.

＜3〉according to＜1〉or＜2 printing ink-media pack, wherein dyestuff is at least a in oil-soluble dyes and the disperse dyes.

＜4〉according to＜1 〉-＜3〉any one printing ink-media pack, wherein inorganic pigment granules is a kind of in titanium dioxide granule, alumina particle and the silica dioxide granule.

＜5 〉, wherein contain polymer in the polymer particles of dyestuff and inorganic pigment microparticles and be at least a in mylar, polyurethane resin, vinylite and the acrylic resin according to＜1 〉-＜4〉any one printing ink-media pack.

＜6〉according to＜1 〉-＜5〉any one printing ink-media pack, the equal particle diameter of body that wherein contains the polymer particles of dyestuff and inorganic pigment microparticles is 5nm-200nm.

＜7〉according to＜1 〉-＜6〉any one printing ink-media pack, wherein water-soluble solvent is glycerine, diethylene glycol (DEG), triethylene glycol, 1,3-butanediol, 1,6-hexylene glycol, propane diols, 1,5-pentanediol, dipropylene glycol, trimethylolpropane and 3-methyl isophthalic acid, at least a in the 3-butanediol.

＜8〉according to＜1 〉-＜7〉any one printing ink-media pack, wherein printing ink-media pack comprises at least a in polyol compound with 8 or more carbon atoms and the glycol ethers compound.

＜9〉a kind of printing ink-media pack comprises:

Ink composite and

Deposit described ink composite thereon with the enforcement recording medium printed,

Wherein said ink composite comprises organic solvent, water and colouring agent, and described colouring agent is water insoluble substantially and be dissolved in described organic solvent,

Colouring agent exists with dispersity and dissolved state in water and organic solvent, (molecular mass cut off) is 50 by molecular cut off, after separating, 000 ultrafiltration is in the amount of the colouring agent of dissolved state, based on the total amount of colouring agent in the ink composite for being not more than 10%, and

Recording medium comprises support and in this support coating on the one side at least, measures by the dynamic scan absorptiometer, and the amount of the ink composite that shifts to this recording medium is 4ml/m in 100ms time of contact ²To 15ml/m ², be 7ml/m in 400ms time of contact ²To 20ml/m ²

＜10〉a kind of ink composite comprises organic solvent, water and colouring agent,

Wherein colouring agent is water insoluble substantially and be dissolved in described organic solvent,

Colouring agent exists with dispersity and dissolved state in water and organic solvent, and is the amount that is in the colouring agent of dissolved state after 50,000 ultrafiltration separates by molecular cut off, based on the total amount of colouring agent in the ink composite for being not more than 10%, and

This ink composite is used for according to＜1 〉-＜9〉any one printing ink-media pack.

＜11〉a kind of print cartridge comprises in container according to＜1 〉-＜9〉ink composite in any one printing ink-media pack.

＜12〉a kind of ink jet recording method, at least comprise the ink jet step, wherein in this ink jet step, to according to＜1 〉-＜9〉ink composite in any one printing ink-media pack applies stimulation, with by spraying this ink composite document image on the recording medium of printing ink-media pack.

＜13〉according to＜12〉ink jet recording method, wherein said stimulation is to be selected from least a in heat, pressure, vibration and the light.

＜14〉a kind of ink-jet recording apparatus, at least comprise the ink jet unit, wherein by this ink jet unit to according to＜1 〉-＜9 ink composite in any one printing ink-media pack applies stimulation, with by spraying this ink composite document image on the recording medium of printing ink-media pack.

＜15〉according to＜14〉ink-jet recording apparatus, wherein said stimulation is to be selected from least a in heat, pressure, vibration and the light.

＜16〉a kind of ink recorded matter is included in according to＜1 〉-＜9〉image that uses on the recording medium of any one printing ink-media pack the ink composite of this printing ink-media pack to form.

Printing ink-media pack according to the present invention comprises ink composite and recording medium, wherein ink composite comprises polymer particles, water-soluble solvent and the water that contains dyestuff and inorganic pigment granules, and under 25 ℃, has the surface tension of 20mN/m-35mN/m, recording medium comprise support and this support at least the one side on coating, measure by the dynamic scan absorptiometer to the pure water amount that this recording medium shifts, 100ms time of contact for being not less than 2ml/m ²And less than 35ml/m ², 400ms time of contact for being not less than 3ml/m ²And less than 40ml/m ²

Can provide the high quality image that has than high color saturation and enough tones according to printing ink-media pack of the present invention.That is, adopt dyestuff, thereby compare the picture rich in detail that can on common paper or specific record paper, obtain having higher coloring with pigment; Adopt inorganic pigment granules, thus the picture rich in detail that is still had higher coloring; This dyestuff and inorganic pigment granules are incorporated in the polymer, thereby printing ink-media pack is provided, when the pure water amount that is shifting in recording medium is not less than 2ml/m at 100ms in time of contact ²And less than 35ml/m ², be not less than 3ml/m at 400ms in time of contact ²And less than 40ml/m ²Low absorbency recording medium on during imaging, this printing ink-media pack allows higher gasproof, and compares also with pigment ink and can form the image with higher coloring, and can not suppress image as water soluble dyestuffs printing ink.

And, for recording medium slow-drying with low absorbency and the fixing problem consuming time of colouring agent, can provide and when being suppressed to pearl, to form printing ink-media pack by the surface tension of ink composite under 25 ℃ being controlled at 20-35mN/m with high-fineness and high quality images.

By following printing ink-media pack, can on support or medium, form the high quality image that has than high color saturation and enough tones, and not diffusion or print through, described printing ink-media pack comprises ink composite and deposits this ink composite thereon to implement recording medium printed, wherein this ink composite comprises organic solvent, water and colouring agent, described colouring agent is water insoluble substantially and be dissolved in organic solvent, this colouring agent exists with dispersity and dissolved state in water and organic solvent, by molecular cut off is 50, after 000 ultrafiltration separates, the amount of colouring agent that is in dissolved state based on the total amount of colouring agent in this ink composite for being not more than 10%, and described recording medium comprise support and this support at least the one side on coating, the amount of the ink composite that shifts to this recording medium by the dynamic scan absorptiometer in conjunction with and its ink composite that is fit to measure, be 4ml/m in 100ms time of contact ²-15ml/m ², be 7ml/m in 400ms time of contact ²-20ml/m ²

At least comprise the ink jet step according to ink jet recording method of the present invention, wherein the ink composite in printing ink-media pack according to the present invention applies stimulation in the ink jet step, to pass through to spray this ink composite document image on the recording medium of printing ink-media pack.

Can form the high quality image that has than high color saturation and enough tones by printing on the recording medium of printing ink-media pack according to the ink composite of printing ink-media pack of the present invention according to ink jet recording method of the present invention.

Ink-jet recording apparatus comprises the ink jet unit at least, wherein applies stimulation according to the ink composite in printing ink-media pack of the present invention by this ink jet unit, to pass through to spray this ink composite document image.

Can form the high quality image that has than high color saturation and enough tones by printing on the recording medium of printing ink-media pack according to the ink composite in printing ink-media pack of the present invention according to ink-jet recording apparatus of the present invention.

Ink recorded matter according to the present invention comprises the ink composite in employing printing ink-media pack, the image that forms on the recording medium according to printing ink-media pack of the present invention.

Can have than high color saturation and enough tones by printing ink-media pack of the present invention according to ink recorded matter of the present invention.

The present invention can solve the problem of this area, and provide printing ink-media pack, this printing ink-media pack is not only on common paper or ink-jet specific record paper, even also can form the high quality image that has than high color saturation and enough tones on the recording medium of low absorbency having, the ink jet recording method, ink-jet recording apparatus and the ink recorded matter that utilize this printing ink-media pack also are provided.

Description of drawings

Fig. 1 is for exemplarily showing the schematic elevational view of the tandem type ink-jet recording apparatus structure that the print cartridge that contains ink composite of the present invention has been installed.

Fig. 2 is the exemplary outline perspective view that is attached to ink-jet recording apparatus of the present invention print cartridge in the past that is presented at.

Fig. 3 is the cross-section front view of Fig. 2 print cartridge.

Fig. 4 is integrated with the outline perspective view of the record cell of record head for exemplary demonstration.

Fig. 5 is the profile front view of heating and fixation facility.

Fig. 6 is for explaining the key diagram that concerns between heating unit and printing.

Fig. 7 is for showing the beam split abosrption spectrogram that is used to explain measurements and calculations dissolving content method.

The specific embodiment

For addressing the above problem, the inventor furthers investigate, and the result has made the present invention.

Promptly, the present invention relates to ink composite, wherein said ink composite comprises organic solvent and colouring agent, described colouring agent is water insoluble substantially and be dissolved in organic solvent, this colouring agent exists with dispersity and dissolved state in water and organic solvent, by molecular cut off is after 50,000 ultrafiltration separates, the amount of colouring agent that is in dissolved state based on the colouring agent total amount in the ink composite for being not more than 10%; And have been found that, when described ink composite is applied to recording medium, can obtain to have high quality image than high color saturation and enough tones, and go up not diffusion or print through at support (medium), described recording medium comprise support and this support at least the one side on coating, measure by the dynamic scan absorptiometer, the amount of the ink composite that shifts to this recording medium is 4ml/m in 100ms time of contact ²-15ml/m ², be 7ml/m in 400ms time of contact ²-20ml/m ²

When as the recording medium with low absorbency of the present invention on during imaging, compare with pigment with water-soluble dye, water-insoluble dyestuff such as oil-soluble dyes and disperse dyes can show more excellent coloring.Described water-insoluble dyestuff can show the dissolubility to organic solvent in printing ink, thereby presents the state of being partly dissolved.Colouring agent total amount in based on printing ink, dissolving content is no more than 10%, more preferably during 0.5%-3%, can prevent the problem of diffusion or print through, and, can obtain to have high quality image than high color saturation and enough tones owing to be partly dissolved intrinsic clear painted of dyestuff.

For regulating the meltage of colouring agent, the selection of organic solvent is important; Be applicable to that the present invention comprises glycerine, trimethylolpropane, glycol ethers, triethylene glycol, propane diols, dipropylene glycol, 1 with the representative examples of organic that prevents excessive wash-out, 3-butanediol, 3-methyl isophthalic acid, 3-butanediol, 2-Pyrrolidone, N-N-methyl-2-2-pyrrolidone N-and have the polyalcohol of 8 or more carbon atoms.

And, even described water-insoluble dyestuff also can cause having the image of the clear coloring suitable with water-insoluble dyestuff on common paper and specific record paper, and resistance to water can be improved to levels of pigment.In addition, light resistance and gasproof can be by being incorporated into dyestuff in the polymer, or preparation has the discrete particles state of inorganic pigment granules and strengthens.

Promptly, ink composite, printing ink-media pack, ink jet recording method and record thing can be provided, even when on the recording medium with low absorbency during imaging, they also can form to compare with pigment ink has the more image of high color saturation and enough tones, and do not have the diffusion, print through as water soluble dyestuffs printing ink or suppress image, described recording medium is in such state: the amount of the ink composite that shifts to this recording medium is 4ml/m in 100ms time of contact ²To 15ml/m ², be 7ml/m in 400ms time of contact ²To 20ml/m ²

In addition, slow-drying and the fixing problem consuming time of colouring agent for the recording medium with low absorbency can provide by the surface tension with ink composite and be controlled at printing ink-media pack that 20-35mN/m is suppressed to pearl.And the viscosity that is adjusted under 25 ℃ in the 5mPas-50mPas scope can make printing ink not sprout wings or Cheng Zhu.

In the present invention, term " Cheng Zhu " refers to the phenomenon of this density unevenness: be injected into ink droplet on the recording medium surface and arrive until subsequently ink droplet and still can not be absorbed into fully in the recording medium at that time in ink mist recording, and be retained in the recording medium surface, and mix with subsequently drop, make part colouring agent adhesion in the printing ink, thereby produce density unevenness.In recent conventional printer, be absorbed in during this phenomenon and the time of contact last relative short 100ms between the quantity of ink in the recording medium and have relation; For example for the green image part, become the pearl level to depend on from spraying Y or C printing ink to spraying C or the Y printing ink, absorb or be transferred to the Y (yellow) in the recording medium or the amount of C (cyan) printing ink.

In the present invention, dispersity and dissolved state adopt the particle diameter of 5nm boundary line level to distinguish.Because the 5nm particle diameter is approximate corresponding to about 50,000 molecular weight in the organic material, and the colouring agent that has greater than 50,000 molecular weight do not account for major part, so this boundary line is rational.The method of distinguishing dispersity and dissolved state can be based on conventional filtration equipment or whizzer; Most preferably use ultrafiltration apparatus.

In the present invention, be after 50,000 ultrafiltration separates preferably by molecular cut off, the content of colouring agent that is in dissolved state based on the colouring agent total amount for not being higher than 10%, 0.5%-3% more preferably.

When the content of dissolved colorants surpasses 10% based on all coloring agent, on recording medium, print the back and move owing to be dissolved in colouring agent in the ink carrier, so diffuse images (emergence) and/or back up (print through) take place unfriendly with the infiltration of carrier.The combination with recording medium is depended in the appearance of these problems, and measures by the dynamic scan absorptiometer when the amount of the ink composite that shifts to recording medium, is 4ml/m in 100ms time of contact ²-15ml/m ², be 7ml/m in 400ms time of contact ²-20ml/m ²The time, the appearance of these problems is tangible.When the content of dissolved colorants is 3%-10% based on all coloring agent, back up (print through) unlikely takes place, but diffuse images (emergence) can take place in allowed band on aforementioned recording medium.When the content of dissolved colorants when agent is no more than 3% based on all coloring, even diffuse images (emergence) and back up (print through) do not take place on aforementioned recording medium yet.Under dissolved state, but the colouring agent typical earth surface reveals excellent more coloring, and when dissolving 0.5% or more colouring agents, even other majority all is under the dispersity, also can obtain enough painted clearly.Therefore, when the content of dissolved colorants when agent is lower than 0.5% based on all coloring, with the recording medium combination in painted being tending towards do not expect aspect dim, although it is still in allowed band.

For the content that makes dissolved colorants in above-mentioned scope, the dissolubility of colouring agent can be by regulating with combination of polymers.Based on the enough adhesivenesses of dyestuff, polymer content can suitably increase or reduce, or type of polymer can be selected aptly.In addition, can with based on solvability, water-retaining property, permeability etc., regulate the dissolubility of colouring agent in conjunction with two or three organic solvent.

Printing ink-media pack

Printing ink-media pack according to the present invention comprises ink composite, recording medium and other optional components.

Described ink composite comprises polymer particles, water-soluble solvent and the water that contains dyestuff and inorganic pigment granules, and has the surface tension of 20mN/m-35mN/m under 25 ℃.

Described recording medium comprises support and in this support coating on the one side at least, measures by the dynamic scan absorptiometer, and the pure water amount that shifts to recording medium is not less than 2ml/m time of contact at 100ms ²And be lower than 35ml/m ², be not less than 3ml/m time of contact at 400ms ²And be lower than 40ml/m ²

Printing ink-media pack according to the present invention comprises ink composite and recording medium, therefore, not only on common paper or ink-jet specific record paper, even has the high quality image that also can obtain on the recording medium of low absorbency to have than high color saturation and enough tones.

Ink composite

Ink composite comprises polymer particles, water-soluble solvent and the water that contains dyestuff and inorganic pigment granules at least, and other optional components such as wetting agent.

Ink composite has 20-35mN/m under 25 ℃, the surface tension of preferred 24-30mN/m.Surface tension in the 20-35mN/m scope can be suppressed to the appearance of pearl, and causes providing and can form the printing ink-media pack with high-fineness and high quality image.

The method of surface tension can be selected from known method aptly; For example, surface tension can adopt surface tensiometer (Kyowa Interface Science Co., CBVP-Z) and the platinum plate measure down at 25 ℃.

The viscosity of ink composite is preferably 5-50mPas under 25 ℃.When viscosity was lower than 5mPas, ink droplet was tending towards spreading wide on recording medium, may cause into the generation of pearl or bleeding, when viscosity is higher than 50mPas, and smaller droplets, portion nozzle may not have ink droplet jet, and it may cause the unordered graph picture.

The polymer particles that contains dyestuff and inorganic pigment granules

The polymer particles that contains dyestuff and inorganic pigment granules is for wherein being encapsulated in dyestuff and inorganic pigment granules the material in the polymer particles, and inorganic pigment granules is encapsulated in the material in the polymer particles that the surface is adsorbed with dyestuff or the combination of these materials.

The equal particle diameter of body that contains the polymer particles of dyestuff and inorganic pigment granules is preferably 5-200nm, more preferably 50-150nm.When the equal particle diameter of body is lower than 5nm, may be difficult to stably keep dispersity, thereby may cause that the cluster of grains coalescence is attended by viscosity and increases, when being higher than 200nm, particle may precipitate.

Dyestuff

Dyestuff can be selected according to using aptly, as long as can be encapsulated into or be adsorbed on the polymer particles.Based on the more excellent containment and the viewpoint of adsorptivity, dyestuff is preferably non-water-soluble and is one of oil-soluble dyes and disperse dyes.Term " water-insoluble " is meant that dyestuff can not be dissolved in the 100 mass parts water with 10 mass parts or more amount under 20 ℃.

Oil-soluble dyes exemplify yellow oil soluble dye, orange oil soluble dye, reddish oil soluble dye, violet oil soluble dye, blue oil soluble dye, green oil soluble dye, black oil soluble dye etc.

The yellow oil soluble dye exemplifies C.I. solvent yellow 5, C.I. solvent yellow 6, C.I. solvent yellow 14, C.I. solvent yellow 16, C.I. solvent yellow 21, C.I. solvent yellow 29, C.I. solvent yellow 33, C.I. solvent yellow 93, C.I. solvent yellow 114, C.I. solvent yellow 151 and C.I. solvent yellow 157.

The orange oil soluble dye exemplifies C.I. solvent orange 2, C.I. solvent orange 7, C.I. solvent orange 55 and C.I. solvent orange 60.

The reddish oil soluble dye exemplifies C.I. solvent red 1, C.I. solvent red 3, C.I. solvent red 8, C.I. solvent red 18, C.I. solvent red 23, C.I. solvent red 24, C.I. solvent red 27, C.I. solvent red 43, C.I. solvent red 48, C.I. solvent red 49, C.I. solvent red 51, C.I. solvent red 52, C.I. solvent red 109, C.I. solvent red 111, C.I. solvent red 122, C.I. solvent red 125, C.I. solvent red 127, C.I. solvent red 130, C.I. solvent red 132, C.I. solvent of red 135, C.I. solvent red 145, C.I. solvent red 146, C.I. solvent red 149, C.I. solvent red 150, C.I. solvent red 151, C.I. solvent red 155, C.I. solvent red 168, C.I. solvent red 176, C.I. solvent red 179, C.I. solvent red 180, C.I. solvent red 181, C.I. solvent red 195, C.I. solvent red 207, C.I. solvent red 218, C.I. solvent red 225 and C.I. solvent red 23 3.

The violet oil soluble dye exemplifies C.I. solvent violet 13, C.I. solvent purple 31, C.I. solvent violet 36, C.I. solvent violet 37, C.I. solvent violet 57 and C.I. solvent violet 59.

The blue oil soluble dye exemplifies C.I. solvent blue 19 4, C.I. solvent blue 25, C.I. solvent blue 35, C.I. solvent blue 36, C.I. solvent blue 38, C.I. solvent blue 44, C.I. solvent blue 63, C.I. solvent blue 67, C.I. solvent blue 70, C.I. solvent blue 78, C.I. solvent blue 83, C.I. solvent blue 87, C.I. solvent blue 94, C.I. solvent blue 19 04, C.I. solvent blue 19 05, C.I. solvent blue 19 32 and C.I. solvent blue 19 36.

The green oil soluble dye exemplifies C.I. solvent blue 3, C.I. solvent blue 5, C.I. solvent blue 7, C.I. solvent blue 20 and C.I. solvent blue 28.

The black oil soluble dye exemplifies C.I. solvent black 3 and C.I. solvent black 27.

The oil-dispersing property dyestuff exemplifies Yellow disperse dye, orange disperse dye, red disperse dyes, purple disperse dyes and blue disperse dye.

Yellow disperse dye exemplifies C.I. disperse yellow 54, C.I. dispersion yellow 64, C.I. disperse yellow 114 and C.I. disperse Yellow 160 150.

Orange disperse dye exemplifies C.I. disperse orange 30.

Red disperse dyes exemplifies C.I. disperse red 22, C.I. disperse red 60, C.I. disperse red 73, C.I. Red-1 200 77 and C.I. disperse Red 35 6.

The purple disperse dyes exemplify C.I. disperse violet 57.

Blue disperse dye exemplifies C.I. Disperse Blue-56, C.I. disperse blue 60, C.I. disperse blue 73, C.I. disperse blue 106 and C.I. disperse blue 165.

Described dyestuff can be non-water-soluble dye, and it can be processed into non-water-soluble by multiple water-soluble dye.Water-soluble dye is processed into non-water-soluble method is preferably based on the formation ionic complex, as cationic surfactant is combined on the anionic dye.

Inorganic pigment granules

Inorganic pigment granules can be selected according to using aptly; Its example comprises titanium dioxide granule, alumina particle, silica dioxide granule, ferric oxide particles, iron hydroxide particle and granules of stannic oxide.In these, preferred especially titanium dioxide granule, alumina particle and silica dioxide granule.

The shape of inorganic pigment granules preferably has low length-width ratio, and is preferred especially spherical.The color of inorganic pigment granules is preferably transparent or white.

The primary particle diameter of inorganic pigment granules preferably is not more than 100nm, more preferably 5-50nm.

Polymer

The polymer that contains in the polymer particles of dyestuff and inorganic pigment granules can be selected from conventional polymer aptly; The example of polymer comprises mylar, polyurethane resin, vinylite, acrylic resin, epoxy resin, olefin resin, polyimide resin, alkyd resins, fluororesin and organic siliconresin.Wherein, owing to polymer particles can be dispersed in the aqueous dispersion medium easily and stably, so preferred polyester resin, polyurethane resin, vinylite and acrylic resin.

Mylar exemplifies those that are prepared by polybasic carboxylic acid and polyalcohol.Polybasic carboxylic acid exemplifies aromatic dicarboxylic acid, aliphatic dicarboxylic acid etc.

The example of aliphatic dicarboxylic acid comprises terephthalic acid (TPA), M-phthalic acid, phthalic acid, 1,5-naphthalene dicarboxylic acids, 2,6-naphthalene dicarboxylic acids, diphenic acid, sulfo group terephthalic acid (TPA), 5-sulfoisophthalic acid, hexahydrophthalic anhydride, 4-sulfosalicylic phthalate, 4-sulfo group naphthalene-2,7-dicarboxylic acids, 5-(4-sulfophenoxy) M-phthalic acid and sulfo group terephthalic acid (TPA).

The example of aliphatic dicarboxylic acid comprises butanedioic acid, adipic acid, azelaic acid, decanedioic acid and dodecanedicarboxylic acid.

Other polybasic carboxylic acid exemplifies aromatic series oxygen yl carboxylic acid, alicyclic dicarboxylic acid, the above polybasic carboxylic acid of ternary.

Polyalcohol exemplifies aliphatic polyol.The example of aliphatic polyol comprises ethylene glycol, propane diols, 1, ammediol, 2, the 3-butanediol, 1, the 4-butanediol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, neopentyl glycol, diethylene glycol (DEG), dipropylene glycol, 2,2,4-trimethyl-1, the 3-pentanediol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, trimethylolethane, trimethylolpropane, glycerine, pentaerythrite, 1, the 4-cyclohexanediol, 1, the 4-cyclohexanedimethanol, the spiroglycol, three ring decanediols, three ring decyl methyl alcohol, the meta-xylene glycol, the ortho-xylene glycol, 1, the 4-Benzenediol, bisphenol-A and lactone PEPA.

Other polyalcohol exemplifies alicyclic polyol and aromatic polyol.

Polyurethane resin exemplify by isocyanates and have can with those of the compound of the functional group of isocyanate reaction.

Polyurethane resin also exemplifies the resin that can prepare with the compound polymerization of the functional group of isocyanate reaction by isocyanates and one or more are had.

Isocyanates exemplifies aliphatic polyisocyante, alicyclic polyisocyanates and aromatic polyisocyanate.

The example of aliphatic polyisocyante comprises ethylidene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, eight methylene diisocyanates and nine methylene diisocyanates.

The example of alicyclic polyisocyanates comprises IPDI, two (isocyanide oxygen ylmethyl) cyclohexane, dicyclohexyl methyl hydride diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate and dicyclohexyl dimethylmethane vulcabond.

The example of aromatic polyisocyanate comprises phenylene vulcabond, trichloro-ethylene vulcabond, ethyl phenylene vulcabond, isopropylidene phenylene vulcabond, dimethyl phenylene vulcabond, diethyl phenylene vulcabond, diisopropyl phenylene vulcabond, trimethylbenzene triisocyanate, benzene triisocyanate, naphthalene diisocyanate, methyl naphthalene vulcabond, biphenyl diisocyanate and tridine vulcabond.

Other isocyanates exemplifies sulfur-bearing aliphatic isocyanates, aliphatic curing isocyanates, aromatic sulphonic acid isocyanates, sulphonic acid ester isocyanates, aromatic sulfonamide and sulfur heterocyclic compound.

Has the condensation reaction products that can exemplify at least a polyalcohol in aliphatic polyol, aromatic polyol and organic acid and aliphatic polyol and the aromatic polyol with the compound of the functional group of isocyanate reaction.

The example of aliphatic polyol comprises ethylene glycol, diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, propane diols, dipropylene glycol, butanediol, neopentyl glycol, glycerine, trimethylolethane, trimethylolpropane, butantriol, 1, the 2-methyl glucoside, pentaerythrite, dipentaerythritol, tripentaerythritol, sorbierite, erythritol, threitol, ribitol, arabite, xylitol, allitol, sweet mellow wine, dodecanol (dodecitol), iditol, ethylene glycol, inositol, hexanetriol, three mannoses, two glycerine (diglyperol), polyethylene glycol, polypropylene glycol, polytetramethylene glycol, three (2-ethoxy) cyanurate, cyclobutanediol, the ring pentanediol, cyclohexanediol, the ring heptandiol, the ring ethohexadiol, the polylactone glycol, cyclohexanedimethanol, the hydroxypropyl cyclohexanol, two cyclohexanediols, phloroglucite, maltitol and lactitol.

The example of aromatic polyol comprises dihydroxy naphthlene, trihydroxynaphthalene, tetrahydroxy naphthalene, dihydroxy benzenes, benzenetriol, connection phenetetrol, pyrogallol, (hydroxyl naphthyl) pyrogallol, trihydroxy phenanthrene, bisphenol-A, Bisphenol F, dimethylbenzene diphenol and two (2-hydroxyl-oxethyl) benzene.

In the condensation reaction products between organic acid and polyalcohol, the organic acid example comprises oxalic acid, glutamic acid, adipic acid, acetate, M-phthalic acid, salicylic acid and PMA.

Have can and other compound of the functional group of isocyanate reaction exemplify addition reaction product, 2 between addition reaction product, alkylene polyamine and alkylene oxide between halogenation polyalcohol, polyalcohol and alkylene oxide such as oxirane and expoxy propane, 2-dihydroxymethyl lactate, 2,2-dihydromethyl propionic acid ester, 2,2-dimethylolpropionic acid ester, 2,2-dihydroxymethyl valerate, 3,4-diaminourea fourth sulfonic acid, 3, the caprolactone modification product of 6-diaminourea-2-toluenesulfonic acid, these compounds, polyamino compound, multi-thioalcohol compound and a-amino acid.These can be separately or two or more be used in combination.

Described vinylite and acrylic resin can be selected according to using aptly; For example, available those that produce by following polymerisable monomer.

Described polymerisable monomer exemplified by vinyl aromatic hydrocarbons, (methyl) acrylate and unsaturated carboxylic acid.

The example of vinyl-arene comprises styrene, o-methyl styrene, a methyl styrene, p-methylstyrene, AMS, to ethyl styrene, 2,4-dimethyl styrene, to t-butyl styrene, to chlorostyrene and divinylbenzene.

The example of (methyl) acrylate comprises methyl acrylate, ethyl acrylate, butyl acrylate, the acrylic acid n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, the acrylic acid n-pentyl ester, the acrylic acid isopentyl ester, the acrylic acid peopentyl ester, acrylic acid 3-(methyl) butyl ester, 2-EHA, cyclohexyl acrylate, Hexyl 2-propenoate, 2-ethyl hexyl acrylate, acrylic acid ester in the ninth of the ten Heavenly Stems, decyl acrylate, acrylic acid undecyl ester, dodecylacrylate, phenyl acrylate, methyl methacrylate, n propyl methacrylate, isopropyl methacrylate, n-BMA, isobutyl methacrylate, the metering system tert-butyl acrylate, the methacrylic acid n-pentyl ester, the metering system isoamyl valerate, the methacrylic acid peopentyl ester, methacrylic acid 3-(methyl) butyl ester, methacrylic acid 2-Octyl Nitrite, hexyl methacrylate, 2-Propenoic acid, 2-methyl-, octyl ester, nonyl methacrylate, decyl-octyl methacrylate, methacrylic acid undecyl ester and lauryl methacrylate.

The example of unsaturated carboxylic acid comprises acrylic acid, methacrylic acid, itaconic acid and maleic acid.

The example of other polymerisable monomer comprises (methyl) acrylamide, N-substituted maleimide amine, maleic anhydride, (methyl) acrylonitrile, vinyl ketone, vinylacetate and vinylidene chloride.

These polymerisable monomers can use separately, and perhaps two or more are used in combination.

Described polymer particles can show excellent water dispersible by ionic group is provided to the surface.

The example of described ionic group comprises sulfonic group, carboxylic acid group, sulfate, phosphonate group and phosphinic acids base, and the uncle of alkali metal salt group, ammonium salt group and these groups is to tertiary amine group.Wherein, the ammonium salt group of the alkali metal salt group of the ammonium salt group of optimization acid's alkali metal salt group, carboxylic acid, sulfonic acid and sulfonic acid.In addition, based on the viewpoint of aqueous dispersion stability, the alkali metal salt group of preferred sulfonic acid and the ammonium salt group of sulfonic acid.

Described ionic group can provide by add the monomer with ionic group when synthesizing described resin.

The salt of ionic group can be ammonium ion, Li, Na, K, Mg, Ca, Cu, Fe etc.Wherein, owing to do not have gas to produce and unlikely produce deposit, therefore more preferably Li, K and Na.

In the present invention, polymer particles can be by disperseing in water in the mode of microencapsulation or emulsification applying hydrophilic polymer on the colouring agent, and described colouring agent is water insoluble substantially and be dissolved in organic solvent.

Use polymer-coated dyestuff or inorganic pigment granules can from conventional method, select aptly with the method for producing particulate, for example, available interface sedimentation and interfacial polymerization.

The interface sedimentation that is applicable to jetted ink specifically can be phase transfer emulsion method or sour sedimentation.

In the phase transfer emulsion method, polymer and water-insoluble dyestuff are dispersed in glassware for drinking water has low compatibility and boiling point to be higher than in the organic solvent of water, with this polymer hydrophiling, carries out emulsification by adding water then, organic solvent is removed in distillation subsequently, thereby is transferred to aqueous phase.

In sour sedimentation, polymer and water-insoluble dyestuff are dispersed in the aqueous medium, with this polymer by adding sour hydrophobization, thereby make this polymer be adsorbed on securely on the water-insoluble dye granule, alkali is added with hydrophiling again in the washing back in this polymer, thereby is dispersed in the aqueous medium.

Specifically, the acid sedimentation is implemented in the following way: described polymer is come hydrophiling by adding alkali compounds neutralizing acid group such as carboxylic acid group, and with the polymer dissolution of this hydrophiling in aqueous medium, to wherein adding pigment and wetting, use then can high-speed stirred homogenizer, grinding and dispersing apparatus such as ball mill and ball mill with ball, kneading and dispersing apparatus such as roller mill by means of shearing force, or ultrasonic dispersing apparatus, handle this mixture, thereby under the state that granules of pigments is encapsulated in the polymer, this granules of pigments is scattered in the aqueous medium.

Described alkali compounds can be, for example, and inorganic compound such as NaOH, potassium hydroxide and lithium hydroxide, or organic amine such as diethanol amine, dimethylethanolamine, triethanolamine, diisopropanolamine (DIPA).

Adding under the situation of surfactant as dispersing aid, the amount of surfactant need be as much as possible little in the scope of not damaging press quality and resistance to water.

Acid is added in the dispersion that obtains, with oxidation carboxylic acid etc. and make polymer water insoluble, thereby with polymer deposition on granules of pigments so that absorption is more firm.In this stage, granules of pigments is deposited in the aqueous medium bottom with the paste state.

Described acid can be for example inorganic acid or organic acid; Inorganic acid can be for example hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid; Organic acid can be for example formic acid or acetate.Acid deposition back pH is preferably 2-6.Preferably Suan amount is not in described acid can cause the scope of polymer property change.

Can adopt suction strainer, pressure filtration or centrifugation with the described paste that neutralizes, and separate this paste and water.The paste of this neutralization is passed through to add alkaline matter hydrophiling once more, to be dispersed in the aqueous medium.Described alkaline matter can be above-mentioned inorganic salts or organic amine.

Can advantageously adopt emulsion polymerization in interfacial polymerization, this method is implemented in atent solvent such as deionized water in the presence of polymerization initiator.Described polymerization initiator can be the redox polymerization initator that adopts persulfate, perborate or peroxide and reducing agent simultaneously.

The example of persulfate comprises potassium hydrogen persulfate, hydrogen persulfate sodium and ammonium persulfate.The example of perborate comprises sodium perborate, potassium perborate and ammonium pertorate.

The example of peroxide comprises above-mentioned persulfate and perborate in the redox polymerization initator.Reducing agent example in redox polymerization comprises sodium sulfite, sodium hydrosulfide and ferrous sulfate.

In emulsion polymerization, reaction temperature can be selected aptly according to the type of reactant and solvent etc.; Preferable reaction temperature is a room temperature to 100 ℃.

In emulsion polymerization, the reaction time can be selected aptly according to the type of reactant and solvent etc.; The preferred reaction time is 3-20 hour.

In emulsion polymerization, after reaction was finished, the polymer emulsion that contains emulsifying agent can by conventional methods as neutralize and obtain.

Comprise the total solid content of the content of dyestuff in the polymer particles of dyestuff and inorganic particles, be preferably 10 quality %-80 quality %, more preferably 20 quality %-60 quality % based on polymer particles.When this content during less than 10 quality %, the color saturation of ink recorded matter and/or image density may be not enough, when this content during greater than 80 quality %, may damage the storage stability of printing ink.Comprise the total solid content of the content of inorganic pigment granules in the polymer particles of dyestuff and inorganic particles, be preferably 5 quality %-60 quality %, more preferably 10 quality %-40 quality % based on polymer particles.

The solid content of polymer particles that comprises dyestuff and inorganic particles is preferably 2 quality %-40 quality %, more preferably 5 quality %-20 quality % based on the total solid content of ink composite.

Water-soluble solvent

Water-soluble solvent is intended to prevent to adopt the ink composite drying of water as liquid medium, and/or strengthens dispersion stabilization.

Water-soluble solvent exemplifies polyalcohol, polyol alkyl ether, polyalcohol aryl ether, nitrogen-containing heterocycle compound, acid amides, amine, sulfur-containing compound, propene carbonate, ethylene carbonate etc.It can use separately, or two or more are used in combination.

The example of polyalcohol comprises glycerine, diethylene glycol (DEG), 1,3-butanediol, 3-methyl isophthalic acid, 3-butanediol, triethylene glycol, propane diols, dipropylene glycol, trimethylolpropane, trimethylolethane, ethylene glycol, diethylene glycol (DEG), dipropylene glycol, tripropylene glycol, tetraethylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, 1,5-pentanediol, 1,6-hexylene glycol, glycerine, 1,2,6-hexanetriol, 1,2,4-butantriol, 1,2,3-butantriol, penta triol (petriol) etc.

The example of polyol alkyl ether comprises ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, dihydroxypropane single-ether etc.

The example of polyalcohol aryl ether comprises ethyleneglycol monophenylether, ethylene glycol monobenzyl ether etc.

The example of nitrogen-containing heterocycle compound comprises 2-Pyrrolidone, N-N-methyl-2-2-pyrrolidone N-, N-ethoxy-2-Pyrrolidone, 1,3-methylimidazole alkane ketone, epsilon-caprolactams, gamma-butyrolacton etc.

The example of acid amides comprises formamide, N-NMF, N, dinethylformamide etc.

The example of amine comprises MEA, diethanol amine, triethanolamine, mono aminoethane, diethylamine, triethylamine etc.

The example of sulfur-containing compound comprises dimethyl sulfoxide (DMSO), sulfolane, thiodiethanol etc.

Wherein, prevent the viewpoint of the excellent effect of bad injection, excellent storage stability and excellent jetting stability based on relying on dissolubility and water evaporates, preferably glycerine, diethylene glycol (DEG), triethylene glycol, 1,3-butanediol, 1,6-hexylene glycol, propane diols, 1,5-pentanediol, dipropylene glycol, trimethylolpropane and 3-methyl isophthalic acid, the 3-butanediol.

Preferred described water-soluble solvent comprises carbohydrate; Described carbohydrate exemplifies monose, disaccharides, compound sugar such as trisaccharide and tetrose and polysaccharide.

The object lesson of described carbohydrate comprises glucose, mannose, fructose, ribose, wood sugar, arabinose, galactolipin, maltose, cellobiose, lactose, sucrose, trehalose, maltotriose etc.

The term polysaccharide refers to the sugar on the wideest meaning of this term, comprises the material that occurring in nature extensively exists, as alpha-cyclodextrin and cellulose.Described steamed bun stuffed with sugar is drawn together the derivative of sugar.The derivative of sugar exemplifies the thio-acid of reduced sugar, oxosugar, amino acid or sugar.

Reduced sugar exemplifies sugar alcohol.Described sugar alcohol can be the compound that following formula is represented.The object lesson of sugar alcohol comprises maltitol and D-sorbite.

HOCH ₂(CHOH) _nCH ₂OH

In following formula, the integer of " n " expression 2-5.

The example of oxosugar comprises glycuronic acid and uronic acid.Wherein, preferred sugar alcohol.

The content of preferred water soluble solvent is 10 quality %-50 quality % based on the total amount of ink composite.When this content is lower than 10 quality %, because printing ink is tending towards making viscosity raise to cause that at the nozzle inner drying ink droplet that sprays may be towards non-rectilinear direction flight or can not ink jet, when this content surpasses 50 quality %, the storage stability possible deviation of printing ink.

The stability that from the beginning ratio of water-soluble solvent and the polymer particles solid content that contains dyestuff and inorganic pigment granules (solid masses in the polymer particles of the quality of water-soluble solvent/contain dyestuff and inorganic pigment granules) appreciable impact printing ink spray.When wetting agent content was low, although contain the solid content height of the polymer particles of dyestuff and inorganic pigment granules, printing ink had still promoted the water evaporates around the nozzle meniscus, may cause defective to be sprayed.

The ratio of water-soluble solvent and the solid content of the polymer particles that contains dyestuff and inorganic pigment granules (solid masses in the polymer particles of the quality of water-soluble solvent/contain dyestuff and inorganic pigment granules) is preferably 0.25-25, more preferably 1-8, preferred especially 2-4.When the ratio of water-soluble solvent and the solid content of the polymer particles that contains dyestuff and inorganic pigment granules was in this scope, ink composite can have very excellent drying property, storage property and reliability.

Wetting agent

When being added into wetting agent in the ink composite, surface tension descends, and has promoted to be applied to the infiltration of the ink droplet on recording medium such as the paper, sprouts wings and/or bleeding thereby can alleviate.

Selective wetting agent aptly as long as it is suitable for the scope of surface tension adjustment to 20-35mN/m, and does not damage dispersed this surfactant with various dyestuffs and water-soluble solvent combination and suits.

The kind of wetting agent can be anion surfactant, nonionic surface active agent etc.

Examples of anionic surfactants comprises polyoxyethylene alkyl ether acetate, dodecyl benzene sulfonate, laruate, polyoxyethylene alkyl ether sulfate salt and fluorine-containing surfactant.

Examples of nonionic surfactants comprises polyalcohol, glycol ethers, polyoxyethylene alkyl ether, polyxyethylated ester, polyoxyethylene sorbitan aliphatic ester, polyxyethylated phenylate, polyoxyethylene alkyl amine, polyoxyethylene alkylamide, acetylenic glycols and fluorine-containing surfactant.

The object lesson of acetylenic glycols surfactant is 2,4,7,9-tetramethyl-5-decine-4,7-glycol, 3,6-dimethyl-4-octyne-3,6-glycol, 3,5-dimethyl-1-hexin-3-alcohol etc.

Described acetylenic glycols surfactant can be the material of commercially available acquisition; Its example comprise Surfynol104,82,465,485 and TG (Air Products Co., USA).Wherein, based on the viewpoint of excellent press quality, preferred Surfynol 465,104 and TG.

The example of fluorine-containing surfactant comprises perfluoroalkyl sulfonate ester, perfluoro carboxylic acid ester, perfluoralkyl phosphate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl betaine, perfluoroalkyl amine oxide and perfluoroalkyl ether compound.

Described fluorine-containing surfactant can be the material of commercially available acquisition; Its example comprises SurflonS-111, S-112, S-113, S-121, S-131, S-132, S-141, S-145 (Asahi Glass Co., Ltd.), Fullard FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (Sumitomo3M Ltd.), Megafac F-470, F1405, F-474 (Dainippon Ink AndChemicals, Inc.), Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR (DuPont), FT-110, FT-250, FT-251, FT-400S (Neos Co.).These can use separately, or two or more are used in combination.

The object lesson of wetting agent is the compound that following formula is expressed.

R ²-O-(CH ₂CH ₂O) _mCH ₂COOM ²General formula (1)

In above-mentioned general formula (1), R ²Expression can have the alkyl with 6-14 carbon atom of side chain; M ²Expression one of alkali metal, quaternary ammonium, quaternary phosphine and alkanolamine; " m " is the integer of 3-12;

General formula (2)

In above-mentioned general formula (2), R ³Expression can have the alkyl with 5-16 carbon atom of side chain; M ³Expression one of alkali metal, quaternary ammonium, quaternary phosphine and alkanolamine;

General formula (3)

In above-mentioned general formula (3), R represents to have the alkyl with 6-14 carbon atom of side chain; " k " is the integer of 5-20.

R ⁵-(OCH ₂CH ₂) ₁OH general formula (4)

In above-mentioned general formula (4), R ⁵Expression can have the alkyl with 6-14 carbon atom of side chain; " 1 " is the integer of 5-20.

General formula (5)

General formula (6)

In above-mentioned general formula (5) and (6), R ' represents to have the alkyl of 6-14 carbon atom independently of one another; " m " and " n " represents 20 or littler integer independently of one another;

General formula (7)

In above-mentioned general formula (7), " p " and " q " represents the integer of 0-40 independently of one another;

General formula (8)

In above-mentioned general formula (8), Rfl represents the group of following general formula (9)-1 or (9)-2 expression.

General formula (9)-1

General formula (9)-2

Described wetting agent preferred water solubleness organic solvent is as polyol compound and glycol ethers compound.Wherein, more preferably adopt at least a in polyol compound with 8 or more carbon atoms and the glycol ethers compound.

When polyol compound had less than 8 carbon atoms, because the permeability deficiency, press quality or image density possibility deterioration were polluted recording medium, and ink composite is expanded not enough on recording medium, thereby the infringement pixel is filled.

The preferred 2-ethyl-1 of polyol compound with 8 or more carbon atoms, 3-hexylene glycol (solubility: 25 ℃ down 4.2%), 2,2,4-trimethyl-1,3-pentanediol (solubility: 25 ℃ down 2.0%) etc.

The glycol ethers compound can be selected according to using aptly; Its example comprises polyol alkyl ether, as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether and dihydroxypropane single-ether; The polyalcohol aryl ether is as ethyleneglycol monophenylether and ethylene glycol monobenzyl ether.

The content of wetting agent can be selected according to using aptly; Preferably, based on the total amount of ink composite, its content is 0.1-10 quality %, more preferably 1 quality %-5 quality %.

Other component

Other component is for example pH conditioning agent, anticorrisive agent/antifungal agent, chelating agent, corrosion inhibitor, resistive connection dirt (kogation) agent, water-soluble ultra-violet absorber, water-soluble infrared absorbent etc.

The pH conditioning agent

Described pH conditioning agent sprays with stable by ink composite is remained alkalescence and the stable dispersion state.When the pH of ink composite was not less than 11, the level of stripping ink gun or inking unit was tending towards obviously, thereby for example problem of printing ink deterioration, seepage or bad injection can occur.

Because the pH conditioning agent of part kind may damage dispersion, therefore preferably the pH conditioning agent was added in the stage of dispersant and dyestuff being mixed and be scattered in the water, rather than mixing and disperseing the back to add with water-soluble solvent, wetting agent etc.

Described pH conditioning agent can be, for example, and hydramine, alkali metal hydroxide, ammonium hydroxide, phosphonium hydroxides and alkali carbonate.These can use separately, and perhaps two or more are used in combination.

The example of described hydramine comprises diethanol amine, triethanolamine, 2-amino-2 ethyl-1, ammediol; The example of alkali metal hydroxide comprises lithium hydroxide, NaOH and potassium hydroxide; The example of ammonium hydroxide comprises ammonium hydroxide and quaternary ammonium hydroxide; The example of phosphonium hydroxides comprises quaternary phosphonium hydroxide; The example of alkali carbonate comprises lithium carbonate, sodium carbonate and potash.

Anticorrisive agent/antifungal agent

The example of anticorrisive agent/antifungal agent comprises sodium dehydroacetate, sodium sorbate, 2-pyridine mercaptan-1-sodium oxide molybdena, Sodium Benzoate and sodium pentachlorophenol.

Chelating agent

The example of chelating agent comprises sodium ethylene diamine tetracetate, sodium nitrilo triacetate, hydroxyethylethylene diamine tri-acetic acid sodium, diethylene-triamine pentaacetic acid sodium and uramil sodium diacelate.

Corrosion inhibitor

The example of antirust agent comprises acid sulphite, sodium thiosulfate, thiodiethanol acid ammonium, nitrous acid diisopropyl ammonium, pentaerythritol tetranitrate and nitrous acid two hexamethylene ammoniums.

Anti-scaling

Fouling can prevent by anti-scaling is mixed in the ink composite.

Fouling is a heat intrinsic problem, in described heat head, apply electric current with instantaneous heating ink composite to heater, and ink composite sprayed by the pressure effect that the ink composite by this heating causes, fouling is meant that the component of ink composite causes that change of properties and the material that obtains stick to the phenomenon on the heater when heating.When causing fouling, use the heating of heater to become unusually, cause more weak expulsion pressure, or under worst condition jet ink composition not.

The example of anti-scaling comprise polyphosphoric acid, polyaminocarboxylic acid, glycuronic acid, hydroxycarboxylic acid, PAPE, these compounds salt, have amino acid or salt and have methyl or the ammonium salt of methylene and carboxyl.

Recording medium

Recording medium comprise support, this support at least the one side on coating and optionally other the layer.

Measure by the dynamic scan absorptiometer to the pure water amount that this recording medium shifts, be not less than 2ml/m time of contact at 100ms ²And be lower than 35ml/m ², preferred 2.5-15ml/m ²When the transfer amount of pure water is lower than 2ml/m time of contact at 100ms ²The time, be easy to into pearl, when being higher than 35ml/m ²The time, the printing ink point of record is compared with the diameter of expectation may be too small.

Measure by the dynamic scan absorptiometer to the pure water amount that this recording medium shifts, be not less than 3ml/m time of contact at 400ms ²And be lower than 40ml/m ², preferred 3.5-25ml/m ²When the transfer amount of pure water is lower than 3ml/m time of contact at 400ms ²The time, because the drying property deficiency is tending towards producing the promoters vestige, when being higher than 40ml/m ²The time, the gloss of dry back image section may be low.

Dynamic scan absorptiometer (DSA, Japan TAPPI Journal, vol.48, in May, 1994,88-92 page or leaf, Shigenori Kuga) is a kind of device that is determined at systemic amount of liquid of utmost point short time.The dynamic scan absorptiometer moves directly to read the mode of the speed that absorbs liquid based on meniscus in the capillary, automatically measure uptake, sample is a dish type, absorb head helical scanning on sample of liquid, sweep speed changes automatically according to preassigned pattern, and each sample is repeated the measurement of necessary number of times.To pass through Teflon to the head of pattern product feed fluid Pipe is connected on the capillary, and reads the position of meniscus in the capillary automatically by optical pickocff.Specifically, the water yield of transfer adopts dynamic scan absorptiometer (K350 series D type, Kyowaseiko Co.) to measure.In the transfer amount of 100ms and 400ms time of contact respectively by determining near insert transfer amount expection time of contact of time of contact measurement result.

Support

Support can be selected according to using aptly; Its example comprises based on the paper of wood fibre with based on the flaky substance such as the adhesive-bonded fabric of timber or synthetic fibers.

Described paper can be selected from conventional paper, and can be by wood pulp or secondary stock production.The example of wood pulp comprises broad leaf tree kraft pulp (LBKP), coniferous tree kraft pulp (NBKP), LBSB, GP and TMP.

The raw material of secondary stock can be as shown in the standard scale (Waste PaperRegeneration Acceleration Center Foundation) of waste paper standard quality: blank sheet of paper limit (johaku), the blank sheet of paper (keihaku) of band color line bar, milky white paper (cream haku), card, extra white paper (tokuhaku), middle blank sheet of paper (chuhaku), single page books and periodicals trimming (mozou), look blank sheet of paper (irohaku), Kent paper, white art paper (shiro art), meticulous side cut paper (tokujogiri), special side cut paper (betsujogiri), newspaper, magazine paper etc.More particularly, waste paper is chemical pulp sheet and the paper that contains high yield paper pulp; Its example comprises printer media such as non-coating accounting machine paper, heat-sensitive paper and impact paper; OA waste paper is as PPC paper; Coated paper is as art paper, coated paper, little coated paper (bitoko paper) and unglazed finish; Non-coated paper as no wood paper, no timber Colored Paper, notebook paper, letter paper, wrapping paper, chromatics paper, contain wood paper, newspaper, grind wood paper, supercalendered paper, single page books and periodicals trimming, pure white machine glazed paper and milk box.These can use separately, or two or more are used in combination.

Secondary stock typically passes through in conjunction with following four step productions.

(1) in the disassociation step, with waste paper with mechanical force and chemical treatments resolving into fiber, and printing-ink is removed from this fiber;

(2) in dust removal step, impurity in the waste paper such as plastics are removed by sieve, cleaner etc.;

(3) in the printing ink step, the printing ink that adopts surfactant to separate from fiber is removed by flotation or cleaning procedure;

(4) in blanching step, make fiber carry out oxidation or reduction, to improve the whiteness of fiber.

When mixed waste paper, based on the total solid content of whole paper pulp, the mixing ratio of waste paper preferably is not more than 40 quality %.This mixing ratio that is not more than 40 quality % can suppress recording medium and curl behind record.

The inner stuffing that is used for support can be conventional Chinese white.The example of Chinese white comprises white inorganic pigment, as precipitated calcium carbonate, powdered whiting, kaolin, clay, talcum, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulphide, zinc carbonate, satin white, alumina silicate, diatomite, calcium silicates, magnesium silicate, synthetic silica, aluminium hydroxide, aluminium oxide, lithopone, zeolite, magnesium carbonate and magnesium hydroxide; And organic Chinese white, as polyglass pigment, acrylics pigment, polyethylene micro-capsule, carbamide resin and melmac.These can use separately, or two or more are used in combination.

The internal sizing agent that is used for support aborning exemplifies neutral rosin sizing agent, alkenyl succinic anhydride (ASA), alkyl ketene dimer (AKD) and petroleum resin sizing agent, and they typically are used to produce neutralized paper; Wherein, preferred neutral rosin sizing agent and alkenyl succinic anhydride.Alkyl ketene dimer can use more on a small quantity because of its higher sizing efficiency, but because record-paper (medium) surface coefficient of friction is tending towards descending, does not therefore expect based on convective viewpoint in the ink mist recording.

Coating

Described coating comprises pigment, adhesive and optionally optional other component such as surfactant.

Described pigment can be the combination of inorganic pigment, inorganic pigment and organic pigment etc.

The example of inorganic pigment comprises kaolin, talcum, powdered whiting, precipitated calcium carbonate, calcium sulfite, amorphous silica, titanium white, magnesium carbonate, titanium dioxide, aluminium hydroxide, calcium hydroxide, magnesium hydroxide, zinc hydroxide and chlorite.

Wherein, the gloss based on excellence produces ability and the ability that the quality that is similar to litho-paper is provided, preferred especially kaolin.

Kaolinic object lesson is the engineering kaolin of layering kaolin, calcined kaolin, surface modification etc.

Preferably have 2 μ m or more the particle of small particle diameter account for 80 quality % or more a high proportion of kaolin content, be 50 quality % or higher based on kaolinic total solid content.

Described kaolin content is preferably 50 mass parts or higher based on 100 mass parts adhesives.When content is lower than 50 mass parts, may be not enough to the influence of gloss level.

The upper limit of this content does not have concrete regulation, and based on kaolinic flowability and the rising of the viscosity under higher shear power especially, preferably this content is not more than 90 mass parts.

Organic pigment can be water-soluble phenylethene-acrylic copolymer particle, SB particle, granules of polystyrene, polyethylene particle etc.These can use separately, or two or more are used in combination.

The content of organic pigment is preferably the 2-20 mass parts based on the whole pigment of 100 mass parts in the coating.

Owing to compare with inorganic pigment, proportion is low relatively, so organic pigment for example can provide that gloss produces the ability excellence, and coating is the effect of high volume, high glaze and surface-coated excellence.

When organic pigment contain quantity not sufficient 2 mass parts the time, these effects can be ignored, when content surpassed 20 mass parts, coating liquid mobile impaired caused lower coating processability and cost uneconomical.

The shape of organic pigment can be selected according to using aptly; For example, described shape can be solid, hollow or annular.Wherein, produce ability, surface-coated ability and mobile viewpoint, preferably have 40% or the hollow shape of higher hollow rate based on the well balanced gloss of coating liquid.Produce ability, surface-coated ability and mobile viewpoint based on the well balanced gloss of coating liquid equally, the average grain diameter of organic pigment is preferably 0.2-3.0 μ m.

Adhesive can be selected according to using aptly; Preferred adhesive is a waterborne polymeric.

Described waterborne polymeric can be for example water-soluble polymer, aqueous dispersion polymers etc.These can use separately, or two or more are used in combination.

Described water-soluble polymer can be selected according to using aptly; Its example comprises polyvinyl alcohol; Anion-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, ethylidene ether modification polyvinyl alcohol; Polyurethane; PVP; The modified polyvinyl pyrrolidones is as PVP-vinyl acetate co-polymer, vinyl pyrrolidone-copolymer of dimethylaminoethyl methacrylate, quaternized vinyl pyrrolidone-copolymer of dimethylaminoethyl methacrylate or vinyl pyrrolidone-Methacrylamide oxypropyl trimethyl ammonium chloride copolymer; Cellulose is as carboxymethyl cellulose, hydroxyethylcellulose and hydroxypropyl cellulose; Modified cellulose is as the cationization hydroxy ethyl fiber; The modification derivant of polyester, polyacrylic acid (ester), melmac or these materials; The synthetic resin of making by the polyester-polyurethane ester copolymer; And other material, as poly-(methyl) acrylic acid, poly-(methyl) acrylamide, oxidized starch, phosphorylated starch, from modified starch, cationic starch, other modified starch, PEO, Sodium Polyacrylate and sodium alginate.Above-mentioned substance can be used alone or in combination.

Wherein, based on the absorbency viewpoint, preferably polyethylene alcohol, cation-modified polyvinyl alcohol, ethylidene ether modification polyvinyl alcohol, polyester, polyurethane and polyester-polyurethane ester copolymer.

Aqueous dispersion polymers can be selected according to using aptly; Its example comprises polyvinyl acetate, polyethylene-polyvinyl acetate copolymer, polystyrene, styrene-(methyl) acrylate copolymer, (methyl) acrylate polymer, polyvinyl acetate-(methyl) acrylate copolymer, SB, ethylene-propylene copolymer, polyvingl ether and organosilicon-acrylic copolymer.

Water-dispersed resin can comprise crosslinking agent or be the self-crosslinking copolymer.Crosslinking agent can be melamine methylol, methylolurea, methylol hydroxy propylidene urea or isocyanates.The self-crosslinking copolymer exemplifies the copolymer with N hydroxymethyl acrylamide unit.

The content of waterborne polymeric is based on 100 mass parts pigment, preferred 2-100 mass parts, more preferably 3-50 mass parts.The amount of waterborne polymeric is defined as making that the water yield that shifts to recording medium drops in the expected range.

When the dyestuff in the ink composite is water dispersible, the cation organic compound can be allocated in the coating according to using.

The cation organic compound can be uncle to tertiary amine, can use monomer, oligomer or the polymer of quaternary ammonium salt, they with water-based ink in direct dyes or the sulfonic group of acid dyes, carboxyl or amino reaction formation insoluble salt.Wherein, preferred uncle is to the oligomer or the copolymer of tertiary amine and quaternary ammonium salt.

The cation organic compound can be dimethylamine-chloropropylene oxide condensation polymer for example, dimethylamine-ammoniacal liquor-chloropropylene oxide condensation product, poly-(trimethyl aminoethyl-methacrylate methylsulfuric acid ester), hydrochloric acid diallylamine-acrylamide copolymer, poly-(hydrochloric acid diallylamine-sulfur dioxide), polysalt acid allylamine, poly-(hydrochloric acid allylamine-hydrochloric acid diallylamine), acrylamide-diallylamine copolymer, the polyvinylamine copolymer, dicyandiamide, dicyandiamide-ammonium chloride-melocol condensation product, polyalkylene polyamine-dicyandiamide ammonium salt condensation product, dimethyl diallyl ammonium chloride, polysalt diene acid propyl methylamine, poly-(diallyldimethylammonium chloride), poly-(diallyldimethylammonium chloride-sulfur dioxide), poly-(diallyldimethylammonium chloride-hydrochloric acid diallylamine derivative), acrylamide-diallyldimethylammonium chloride copolymer, acrylate-acrylamide-hydrochloric acid diallylamine copolymer, polyaziridine, aziridine derivative such as allylamine polymer and modification polyaziridine alkylene oxide.These can use separately, or two or more are used in combination.

The cation organic compound that wherein preferably will have lower molecular weight is used in combination with the another kind of cation organic compound with higher molecular weight.Cation organic compound with lower molecular weight can cause improving image density and reduce emergence with the combination with another kind of cation organic compound of higher molecular weight.

Have cation organic compound preference such as the dimethylamine-chloropropylene oxide condensation polymer or the polysalt acid allylamine of lower molecular weight, the cation organic compound preference with higher molecular weight is as poly-(diallyldimethylammonium chloride).

The cation equivalent of cation organic compound is preferably 3-8meq/g according to colloid titration method (adopting potassium sulfate and toluidine blue).The cation organic compound of this scope can cause the preferable range of following dry deposition amount.

In measurement, the cation organic compound with distilled water diluting to 0.1 quality % solid content, and is not regulated pH according to the cation equivalent of colloid titration method.

The dry deposition amount of cation organic compound is preferably 0.3-2.0g/m ²Between.When the dry deposition amount of cation organic compound is lower than 0.3g/m ²The time, improving image density and/or reduce the effect of sprouting wings may be not enough.

Surfactant

When adding surfactant in the coating, can improve the resistance to water of image, improve image density and alleviate and ooze out.

Surfactant can be selected aptly according to purpose; Surfactant can maybe can use nonionic surface active agent for anion surfactant, cationic surfactant, amphoteric surfactant.Wherein, preferred especially nonionic surface active agent.

Nonionic surface active agent exemplifies the higher alcohol ethylene oxide adduct, the alkyl phenol ethylene oxide adduct, the aliphatic acid ethylene oxide adduct, the polyol fatty acid ester ethylene oxide adduct, the high fatty amine ethylene oxide adduct, the fatty acid amide ethylene oxide adduct, the fat oil ethylene oxide adduct, the ethylene oxide adduct of fat, the polypropylene glycol ethylene oxide adduct, fatty acid glyceride, pentaerythritol fatty ester, sorbierite-sorbitan aliphatic ester, sucrose fatty ester, polyol alkyl ether and alkanolamine fatty acid amide.These can be used alone or in combination.

Polyalcohol can be selected according to using aptly; Its example comprises glycerine, trimethylolpropane, pentaerythrite, sorbierite and monose.

Above-mentioned ethylene oxide adduct can be that ethylene oxide segment is replaced to keeping those of water-soluble degree with alkylene oxide such as expoxy propane and epoxy butane.

The replacement rate of alkylene oxide preferably is not more than 50% in ethylene oxide adduct.The HLB of nonionic surface active agent (hydrophilic ratio) is preferably 4-15, more preferably 7-13.

The content of surfactant is preferably the 0-10 mass parts, more preferably the 0.1-1.0 mass parts based on the above-mentioned cation organic compound of 100 mass parts.

Optionally, can add other optional components in the described coating.Described other component can be alumina powder, pH conditioning agent, anticorrisive agent, antioxidant or other additive.

The method that forms described coating can be selected according to using aptly, and promptly coating can form by dipping on support or coating coating liquid.

Dipping or the method that applies described coating liquid can be selected according to using aptly; For example, described coating can be shifted sizing applicator, doctor knife coater, rod by multiple coating equipment such as conventional sizing applicator, door roller sizing applicator, film and be coated with machine, Kohler coater, curtain coater and implement, perhaps, adopt the conventional sizing applicator, door roller sizing applicator or the film that are equipped on the paper machine to shift sizing applicator dipping or coating coating liquid.Wherein, the finishing technique on machine is rational economically.

The deposition of described coating liquid can be selected according to using aptly; Preferably, deposition is counted 0.5-20g/m with solid ², more preferably 1-15g/m ²If necessary in dipping or after applying with the coating drying.Baking temperature can be selected aptly; Preferred temperature is 100 ℃-250 ℃.

Recording medium can provide backing layer at the back side of support; In addition, between support and backing layer, can form other layer, or can on coating, form protective layer.These layers can be single or multiple lifts.

Print cartridge

Print cartridge of the present invention has the ink composite of printing ink-media pack of the present invention and other optional feature optionally in container.

Described container without limits, can be selected according to purpose aspect its shape, structure, size and material aptly; Preferred its example is by aluminium lamination press mold or the film formed China ink bag of resin.

Ink-jet recording apparatus and ink jet recording method

Ink-jet recording apparatus of the present invention has ink jet unit and other option unit at least, as stimulating generation unit and control module.

Ink jet recording method of the present invention comprises ink jet step and other optional step at least, produces step and control step as stimulating.Ink jet recording method of the present invention can be implemented aptly by ink-jet recording apparatus of the present invention; The ink jet step can be implemented aptly by the ink jet unit; Other step can be implemented aptly by other unit.

Print cartridge of the present invention, ink jet recording method and ink-jet recording apparatus will illustrate with reference to the accompanying drawings, but following explanation only relates to a part of embodiments of the present invention, limits the present invention never in any form.

Fig. 1 is mechanism's schematic elevational view partly that the series connection ink-jet recording apparatus of print cartridge wherein is installed, and described print cartridge is equipped with the record liquid receiver that contains ink composite of the present invention.

The mechanism of this ink-jet recording apparatus partly has following structure: essentially horizontally crossbearer is between the

side plate

1 and 2 of both sides for main support guide rod 3 and secondary support guide rod 4, and balladeur train unit 5 supports in the mode that is free to slide on main scanning direction by main support rod 3 and secondary support bar 4.This balladeur train unit 5 is combined with four jet face 6a (nozzle face) ink gun 6 down therein, and described ink gun 6 sprays Yellow ink (Y), magenta ink (M), cyan ink (C) and black ink (Bk) respectively.At the upside of the ink gun 6 of balladeur train unit 5, four

print cartridge

7y, 7m, 7c and 7k supplying with printing ink to four statures 6 are installed removably.

Below with reference to Fig. 2 and 3 explanation print cartridges 7.Fig. 2 is installed to the tape deck external perspective view of print cartridge before; Fig. 3 is the normal cross-section of print cartridge.

As shown in Figure 3, print cartridge 7 has box body 41, and this box body 41 comprises the printing ink absorbing means 42 that absorbs particular color printing ink.Described box body 41 forms the upper opening that cover unit 44 adheres to or be soldered to shell 43, and the mechanograph for for example being made by resin molded body.Printing ink absorbing means 42 is made by porous body such as polyurethane foam etc., and it embeds box body 41 backs in compression and absorbs printing ink.

The shell 43 of box body 41 has base portion, and this base portion forms has ink supply port 45 from printing ink to record head 6 that supply with, and described ink supply port 45 has the inner circumference with sealing ring 46 couplings.Cover unit 44 has atmosphere opening 47.

For prevent before filling when handle Inkjet Cartridge with filling or transportation in ink supply port 45 when stopping up, or during the vacuum packaging when wide sidewall is exerted pressure, interior oil ink leakage because of the compression of shell 43 may cause is installed in cap member 50 on the box body 41.

As shown in Figure 2, atmosphere opening 47 usefulness oxygen permeabilities are 100ml/m ²Or bigger film shape seal member 55 is sealed on the cover unit 44 and seals.Seal member 55 has the size of a plurality of grooves 48 that can seal atmosphere opening 47 and form around atmosphere opening 47.With oxygen permeability is 100ml/m ²Or bigger seal member 55 sealing atmosphere openings 47 can bring the effect of the degassing level that strengthens printing ink, even because when in the space A (referring to Fig. 3) of printing

ink absorbing means

42 and 41 formation of box body, existing atmosphere to make air dissolves in printing ink, also can under reduced pressure pack print cartridge 7, make air in the described printing ink be expelled to box body 41 and be arranged in the space between the package member of box body 41 outsides with condition of high vacuum degree through seal member 55 by using the package member of making by air-locked aluminium lamination press mold etc.

Fig. 4 has shown printing ink receiver with the ink composite that wherein is filled with printing ink-media pack of the present invention and has been used for the formation example of recording box of the head part of injection record liquid.Specifically, record cell 30 is a tandem type, major part by ink gun 6, wherein receive the cover that the China ink jars 41 of the ink composite be supplied to ink gun 6 and being used to seals China ink jars 41 and constitute.Ink gun 6 has the nozzle 32 of a plurality of jet ink compositions.Ink composite is delivered to public liquid chamber (not shown) by inking pipe (not shown) from China ink jar 41, and according to spraying from nozzle 32 by the signal of telecommunication of tape deck body from electrode 31 inputs.The record cell of the type is called so-called heat or bubble type, and it can pass through its intrinsic structure at lower cost, promptly is applicable to the structure production of the head with heat energy drive source.

Even the ink composite in printing ink-media pack of the present invention also can show jetting stability and frequency stability on a small quantity, and excellent security, thereby, therefore be very suitable owing to the wettability of in heat or the recording method of bubble type, having improved thermal element.

In the foregoing description, the tandem type ink-jet recording apparatus has been described; Also can be applicable to have in the ink-jet recording apparatus of so-called line head according to ink composite of the present invention, wherein nozzle is with for example Z-shaped mode random arrangement, wherein by integrated equal or for the density of the part of target image resolution ratio with arrangement of nozzles for wide with recording medium or be wider than recording medium.

Described ink-jet recording apparatus is not limited to the output printer that PC or digital camera are used, but can also be for comprising the multi-function device of facsimile machine, scanner, phone and its combination.

Heater

Can be equipped with the heat fixer equipment that is used to promote the ink composite photographic fixing according to tape deck of the present invention.Described heat fixer equipment will be at arranging that wherein a plurality of line ink guns and the structure that is installed on the recording equipment describe.

In Fig. 5, promoters 74 is a kind of assembly, and wherein several thin gear-shaped metal parts are attached has the space between this metal parts on an axle, and this promoters 74 with the direction rotation consistent with conveyer belt 40 to discharge recording medium.Described promoters 74 functions as follows: leader record medium in printing and transmission, so that the leading edge of recording medium can not disturbed for example parts of printer cover, and steadily discharge recording medium, and the driving force by using this promoters 74 is in printing with transmit the trailing edge of guaranteeing to promote recording medium in discharging, with its discharge.The existence of promoters 74 can prevent from because promoters 74 contacts and roll extrusion on the print surface of recording medium with the print surface of recording medium, therefore the promoters stain may occur when ink setting is slow simultaneously as paperboard and the bad problem of transmission.

Heat fixer equipment 76 is providing near record head 70B and in the downstream of this record head 70B relatively along transfer path as shown in Figure 5.In this embodiment, the thermal-radiating reflecting plate 82 of halogen heater 84 and reflection halogen heater 84 plays for example effect of hot type printing ink fixation facility 76.Thereby, according to the embodiment of the present invention, realized noncontact heating to recording medium (paper Pa) print surface.That is, implement owing to heat from the top on printing zone surface, but so volatile component in the printing ink such as water efficient drying.As hot type printing ink fixation facility 76, the heating part separating component 86 that provide the thermal-radiating reflecting plate 82 of halogen heater 84 as heating part, reflection halogen heater 84, halogen heater 84 is separated with transfer path and make record head 70B and the adiabatic apparatus 78 of halogen heater 84 thermal insulation with the heat arrival record head 70B that avoids heater 84.

Ink recorded matter

Ink recorded matter of the present invention is for by those of ink-jet recording apparatus of the present invention or ink jet recording method of the present invention record.

Ink recorded matter of the present invention has the image that adopts the ink composite in this printing ink-media pack to form on the recording medium of printing ink-media pack of the present invention.

Recording medium can be selected according to using aptly, and can be similar with aforementioned recording medium.These can use separately, or two or more are used in combination.

Ink recorded matter of the present invention is formed by ink composite, this ink composite comprises polymer particles, water-soluble solvent and the water that contains dyestuff and inorganic pigment granules, and under 25 ℃, has the surface tension of 20mN/m-35mN/m, recording medium comprise support and this support at least the one side on coating, measure by the dynamic scan absorptiometer, the pure water amount that shifts in recording medium time of contact at 100ms is not less than 2ml/m ²And be lower than 35ml/m ², the pure water amount that shifts in recording medium time of contact at 400ms is not less than 3ml/m ²And be lower than 40ml/m ², therefore, even have the high quality image that also can obtain on the recording medium of low absorbency having than high color saturation and enough tones.In addition, in colored printing, there is the effect that improves color of light brightness (brightness) or color saturation (freshness).

Ink recorded matter of the present invention can be advantageously used in multiple application as in the document or written material that write down various printings or image thereon.

Embodiment

The present invention describes reference example, but the present invention should not be limited to this fully.

The preparation of polymer

Be prepared as follows three kinds of polymer.

Polymer 1:

The styrene acrylic base polymer (ProductName: Johncryl 586, Johnson Polymer Co., the matter average molecular weight: 4,600, glass transition temperature Tg: 60 ℃)

Polymer 2:

The raw material that is shown as branch is down packed in the 2L four neck flasks that are equipped with water out, thermometer, nitrogen inlet and agitator, this mixture was heated to 180 ℃ through 3 hours, dewater simultaneously causing dehydration condensation, thus the synthesizing polyester resin.

Composition

Cardura E-10P

^{* 1)}10 mass parts

Adipic acid 27 mass parts

Hexahydrophthalic anhydride 42 mass parts

Neopentyl glycol 2 mass parts

Trimethylolpropane 26 mass parts

Titanium dioxide two fourth tin 0.1 mass parts

^*1) material name: epoxy decylate, Japan Epoxy Resin Co

Polymer 3

Pack into and be equipped with in the four neck flasks of thermometer, nitrogen inlet, agitator and reflux condenser being shown as the branch raw material down, and heat this mixture to react 3 hours down at 80 ℃, add 0.01 mass parts dibutyl tin dilaurate then, under uniform temp, further to react 5 hours.After making the reactant cooling, add the ethylenediamine of 1 mass parts, and make this mixture reaction 1 hour, thus the synthesis of polyurethane resin.

Composition

MEK 90 mass parts

2,2-dihydromethyl propionic acid 13 mass parts

Polylactone glycol 52 mass parts

IPDI 35 mass parts

The preparation of abrasive (Mill Base)

The composition of abrasive (C-1)

Solvent blue 44 ^{* 1)}15 mass parts

Silicon dioxide microparticle

^{* 2)}5 mass parts

Polymer 1 15 mass parts

Deionized water 65 mass parts

^*1) oil-soluble cyan dye Savinyl Cyan GLS, Clariant Japan Co.

^*2)Aerosil-RX200，Japan?Aerosil?Co.

In polymer 1, add 2-amino-2-methyl-1, ammediol, and this mixture is dissolved in the water, be added in this solution above-mentioned oil-soluble dyes solvent blue 44 and silicon dioxide microparticle also fully wetting then, this dispersion is poured in the kneader device (Dyno-mill KDL A type, WAB Co.), and 2,000rpm mediated 40 minutes down, was filled with the zirconium oxide bead of diameter 0.5mm in this kneader device.Add the HCl of 3 mass parts 1N, and stir,, then this mixture is separated into pigment paste and water with whizzer, and removes supernatant to deionized water that wherein adds 400 mass parts and fully stirring with the abrasive that obtains.Repeat this process for several times, add 1.0 mass parts 2-amino-2-methyls-1 as alkali compounds in this creme, ammediol reuses Dyno-mill KDLA type and mediates this mixture.The product of collect mediating, and be that the filter of 1 μ m filters with the aperture, thereby production has the abrasive C-1 of 15 quality % dye strengths.

The composition of abrasive (C-2)

Solvent blue 70 ^{* 1)}15 mass parts

Alumina particulate

^{* 2)}3 mass parts

Polymer 1 15 mass parts

Deionized water 67 mass parts

^*1) oil-soluble cyan dye Oleosol Fast Blue ELN, Taoka Chemical Co.

^*2)APK-G008，Sumitomo?Chemical?Co.

Abrasive C-2 with 15 quality % dye strengths adopts the mode identical with abrasive C-1 by mentioned component production.

The composition of abrasive (C-3)

Abrasive C-3 with 15 quality % dye strengths adopts the mode identical with abrasive C-2 to produce, except the slurry alumina particulate becomes titanium dioxide fine particles (PT-401M, Ishihara Sangyo KaishaLtd.).

The composition of abrasive (C-4)

Pigment blue 15: 3 ^{* 1)}15 mass parts

Dispersant

^{* 2)}5 mass parts

Deionized water 80 mass parts

^*1) organic pigment ECB-301, Dainichiseika Color ﹠amp; Chemicals Mfg.Co.

^*2) be expressed from the next:

C ₁₂H ₂₅-O-(CH ₂CH ₂O) ₄₂-H

Abrasive C-4 with 15 quality % dye strengths adopts the mode identical with abrasive C-1 by mentioned component production.

The composition of abrasive (K-1)

Solvent black 3 ^{* 1)}15 mass parts

Dispersant

^{* 2)}5 mass parts

Deionized water 80 mass parts

^*1) oil-soluble dyes Oil Black 860, Orient Chemical Industries Ltd.

^*2) be expressed from the next:

C ₁₂H ₂₅-O-(CH ₂CH ₂O) ₄₂-H

Abrasive K-1 with 15 quality % dye strengths adopts the mode identical with abrasive C-1 by mentioned component production.

The composition of abrasive (Y-1)

Disperse Yellow 160 150 ^{* 1)}15 mass parts

Polymer 2 15 mass parts

Deionized water 70 mass parts

^*1) disperse dyes Plast Yellow 8050, Arimoto Chemical Co.

In polymer 2, add 2-amino-2-methyl-1, ammediol, and this mixture is dissolved in the water, then above-mentioned oil-soluble dyes solvent red 49 is added in this solution also fully wetting, this dispersion is poured in the kneader device (Dyno-mill KDL A type, WAB Co.), and 2,000rpm mediated 60 minutes down, was filled with the zirconium oxide bead of diameter 0.5mm in this kneader device.Add the HCl of 3 mass parts 1N, and stir,, then this mixture is separated into pigment paste and water with whizzer, and removes supernatant to deionized water that wherein adds 400 mass parts and fully stirring with the abrasive that obtains.After repeating this process several, add the 2-amino-2-methyl-1 of 1.0 mass parts as alkali compounds in this creme, ammediol uses Dyno-mill KDL A type to mediate this mixture once more.The product of collect mediating, and be that the filter of 1 μ m filters with the aperture, thereby production has the abrasive Y-1 of 15 quality % dye strengths.

The composition of abrasive (Y-2)

Disperse Yellow 160 150 ^{* 1)}15 mass parts

Alumina particulate

^{* 2)}3 mass parts

Polymer 2 15 mass parts

Deionized water 67 mass parts

^*1) Yellow disperse dye Plast Yellow 8050, Arimoto Chemical Co.

^*2)APK-G008，Sumitomo?Chemical?Co.

Abrasive Y-2 with 15 quality % dye strengths adopts the composition production of the mode similar to abrasive C-1 by above-mentioned abrasive Y-2.

The composition of abrasive (M-2)

Solvent red 218 ^{* 1)}16 mass parts

Silicon dioxide microparticle ^{* 2)}8 mass parts

Polymer 2 16 mass parts

Deionized water 60 mass parts

^*1) oil-soluble magenta dye Oleosol Fast Pink FB, Taoka Chemical Co.

^*2)Aerosil-RX200，Japan?Aerosil?Co.

Abrasive M-2 with 15 quality % dye strengths adopts the composition production of the mode similar to abrasive C-1 by above-mentioned abrasive M-2.

The composition of abrasive (M-3)

Solvent red 218 ^{* 1)}16 mass parts

Titanium dioxide fine particles ^{* 2)}4 mass parts

Polymer 3 16 mass parts

Deionized water 64 mass parts

^*1) oil-soluble magenta dye Oleosol Fast Pink FB, Taoka Chemical Co.

^*2)PT-401M，Ishihara?Sangyo?Kaisha?Ltd.

Abrasive M-3 with 15 quality % dye strengths adopts the composition production of the mode similar to abrasive C-1 by above-mentioned abrasive M-3.

The dyestuff that obtains for containing of producing in abrasive and the polymer beads of inorganic pigment granules are measured the equal particle diameter of body; The results are shown in the table 1.Measure and adopt UPA150 (Microtrac Co.) to carry out.

The composition of abrasive (M-7)

Solvent red 218 ^{* 1)}15 mass parts

Dispersant

^{* 2)}5 mass parts

Deionized water 80 mass parts

^*1) oil-soluble dyes Oleosol Fast Pink FB, Taoka Chemical Co.

^*2) be expressed from the next

On the basis of above-mentioned abrasive composition, dispersant is dissolved in the deionized water, then to wherein adding oil-soluble dyes and fully wetting, then this mixture is mediated in kneader device (Dyno-mill KDL A type, WAB Co.), and 2,000rpm mediated 60 minutes down, be filled with the zirconium oxide bead of diameter 0.5mm in this kneader device, collect then and filter this kneading material, thereby produce abrasive M-7 with 15 quality % dye strengths with the filter of aperture 1 μ m.

The composition of abrasive (M-8)

Abrasive M-8 with 15 quality % dye strengths adopts the mode identical with abrasive M-7 to produce, except dispersant being become the material with following structural formula.

C ₁₂H ₂₅-O-(CH ₂CH ₂O) ₄₂-H

The composition of abrasive (M-9)

Solvent red 49 ^{* 1)}15 mass parts

Silicon dioxide microparticle

^{* 2)}5 mass parts

Polymer 3 15 mass parts

Deionized water 65 mass parts

^*1) oil-soluble dyes Oil Pink 312, Orient ChemicalIndustries, Ltd.

^*2)Aerosil-RX200，Japan?Aerosil?Co.

With 2-amino-2-methyl-1, ammediol is added in the polymer 3, and it is this mixture is water-soluble, then above-mentioned oil-soluble dyes solvent red 49 and silicon dioxide microparticle are added in this solution, and fully wetting, adopt with the similar mode of abrasive Y-1 then and produce abrasive M-9 with 15 quality % dye strengths.

Table 1

Abrasive	Dyestuff	Inorganic pigment granules	Polymer	The equal particle diameter of body (nm)
Abrasive	Dyestuff	Inorganic pigment granules	Polymer	The equal particle diameter of body (nm)	C-1	Solvent blue 44	Silica	Styrene-propene acyl (polymer 1)	61
Y-2	Disperse Yellow 160 150	Aluminium oxide	Polyester (polymer 2)	98	C-1	Solvent blue 44	Silica	Styrene-propene acyl (polymer 1)	61
Y-2	Disperse Yellow 160 150	Aluminium oxide	Polyester (polymer 2)	98	M-2	Solvent red 218	Silica	Polyester (polymer 2)	155
M-3	Solvent red 218	Titanium dioxide	Polyurethane (polymer 3)	124	M-2	Solvent red 218	Silica	Polyester (polymer 2)	155
M-3	Solvent red 218	Titanium dioxide	Polyurethane (polymer 3)	124	M-6	Solvent red 218	Titanium dioxide	Polyurethane (polymer 3)	235

The preparation of ink composite 1

The composition of ink composite 1

Abrasive C-1 40 mass parts

Glycerine 6 mass parts

1,3-butanediol 18 mass parts

Surfactant

^{* 1)}2 mass parts

3-methyl-2,4-heptandiol 2 mass parts

Proxel LV ^{* 2)}0.1 mass parts

Deionized water 31.9 mass parts

^*1) be expressed from the next:

C ₁₃H ₂₇-O-(CH ₂CH ₂O) ₃-CH ₂COONa

^*2) anticorrisive agent/antifungal agent, Avecia Co.

With glycerine, 1,3-butanediol, 3-methyl-2, surfactant that 4-heptandiol, following formula are represented and ProxelLV are dissolved in the deionized water with the preparation carrier, this carrier is mixed with abrasive (C-1), then the filter of this mixture with average pore size 1 μ m filtered, thereby produce ink mist recording cyan ink (ink composite 1).

The preparation of ink composite 2

The composition of ink composite 2

Abrasive M-2 50 mass parts

Glycerine 9 mass parts

N-N-methyl-2-2-pyrrolidone N-18 mass parts

FT-110 ^{* 1)}1 mass parts

3-methyl-2,4-heptandiol 2 mass parts

Proxel LV ^{* 2)}0.1 mass parts

Deionized water 19.9 mass parts

^*1) fluorine-containing surfactant, Neos Company Ltd.

^*2) anticorrisive agent/antifungal agent, Avecia Co.

Ink mist recording adopts the mode similar to above-mentioned ink composite 1 to be prepared by above-mentioned ink composition with magenta ink (ink composite 2).

The preparation of ink composite 3

The composition of ink composite 3

Abrasive Y-2 50 mass parts

Glycerine 9 mass parts

1,3-butanediol 18 mass parts

Surfactant

^{* 1)}2 mass parts

2,2,4-trimethyl-1,3-pentanediol 2 mass parts

Proxel LV ^{* 2)}0.1 mass parts

Deionized water 18.9 mass parts

^*1) be expressed from the next:

C ₁₃H ₂₇·O·(CH ₂CH ₂O) ₈H

^*2) anticorrisive agent/antifungal agent, Avecia Co.

Ink mist recording adopts the mode similar to above-mentioned ink composite 1 to be prepared by above-mentioned ink component with Yellow ink (ink composite 3).

The preparation of ink composite 4

The composition of ink composite 4

Abrasive M-3 50 mass parts

Glycerine 9 mass parts

1,3-butanediol 18 mass parts

Surfactant

^{* 1)}2 mass parts

2,2,4-trimethyl-1,3-pentanediol 2 mass parts

Proxel LV ^{* 2)}0.1 mass parts

Deionized water 18.9 mass parts

^*1) be expressed from the next:

C ₁₃H ₂₇-O-(CH ₂CH ₂O) ₈H

^*2) anticorrisive agent/antifungal agent, Avecia Co.

Ink mist recording adopts the mode similar to above-mentioned ink composite 1 to be prepared by above-mentioned ink composition with magenta ink (ink composite 4).

The preparation of ink composite 5

The composition of ink composite 5

Abrasive C-1 50 mass parts

Glycerine 9 mass parts

The 3-methyl isophthalic acid, 3-butanediol 18 mass parts

FT-110 ^{* 1)}1 mass parts

3-methyl-2,4-heptandiol 2 mass parts

Proxel LV ^{* 2)}0.1 mass parts

Deionized water 19.9 mass parts

^*1) fluorine-containing surfactant, Neos Company Ltd.

^*2) anticorrisive agent/antifungal agent, Avecia Co.

Ink mist recording adopts the mode similar to above-mentioned ink composite 1 to be prepared by above-mentioned ink composition with cyan ink (ink composite 5).

The preparation of ink composite 6

The composition of ink composite 6

Abrasive C-1 50 mass parts

Glycerine 9 mass parts

1,6-hexylene glycol 18 mass parts

Proxel LV ^{* 1)}0.1 mass parts

Deionized water 22.9 mass parts

^*1) anticorrisive agent/antifungal agent, Avecia Co.

Ink mist recording adopts the mode similar to above-mentioned ink composite 1 to be prepared by above-mentioned ink composition with cyan ink (ink composite 6).

The preparation of ink composite 7

The composition of ink composite 7

Direct blue 199 ^{* 1)}9 mass parts

Glycerine 9 mass parts

The 3-methyl isophthalic acid, 3-butanediol 18 mass parts

FT-110 ^{* 2)}1 mass parts

3-methyl-2,4-heptandiol 2 mass parts

Proxel LV ^{* 3)}0.1 mass parts

Deionized water 60.9 mass parts

^*1) cyan dye Irgasperse Jet Cyan RL, Ciba Specialty Chemicals Inc.

^*2) fluorine-containing surfactant, Neos Company Ltd.

^*3) anticorrisive agent/antifungal agent, Avecia Co.

With the direct indigo plant 199 of direct dyes, glycerine, 3-methyl isophthalic acid, 3-butanediol, 3-methyl-2,4-heptandiol, FT-110 and Proxel LV are dissolved in the deionized water, adopt the filter of average pore size 0.5 μ m to filter this solution then, thereby produce ink mist recording cyan ink (ink composite 7).

The composition of abrasive (M-4)

Solvent red 218 ^{* 1)}14 mass parts

Dispersant ^{* 2)}4 mass parts

Deionized water 82 mass parts

^*1) oil-soluble magenta dye Oleosol Fast Pink FB, Taoka Chemical Co.

^*2) be expressed from the next:

Dispersant is dissolved in the deionized water, then oil-soluble dyes are mixed in this solution also fully wetting, and pour dispersion into kneader device (Dyno-mil KDL A type, WAB Co.) in, be filled with the zirconium oxide bead of diameter 0.5mm in this kneader device, and 2,000rpm mediated 2 hours down, to produce abrasive (M-4).

The preparation of ink composite 8

The composition of ink composite 8

Abrasive M-4 50 mass parts

Glycerine 9 mass parts

1,3-butanediol 18 mass parts

Surfactant

^{* 1)}2 mass parts

2,2,4-trimethyl-1,3-pentanediol 2 mass parts

Proxel LV ^{* 2)}0.1 mass parts

Deionized water 18.9 mass parts

^*1) be expressed from the next:

C ₁₃H ₂₇-O-(CH ₂CH ₂O) ₈H

^*2) anticorrisive agent/antifungal agent, Avecia Co.

Ink mist recording adopts the mode similar to above-mentioned ink composite 1 to be prepared by above-mentioned ink composition with magenta ink (ink composite 8).

The composition of abrasive (M-5)

Pigment violet 19 ^{* 1)}14 mass parts

Dispersant 4 mass parts

Deionized water 82 mass parts

^*1) magenta pigment CROMOPHTAL Red 2020, Ciba Specialty Chemicals Inc.

^*2) be expressed from the next:

Abrasive M-5 adopts the composition production of the mode similar to abrasive C-1 by above-mentioned abrasive M-5.

The preparation of ink composite 9

The composition of ink composite 9

Abrasive M-5 50 mass parts

Glycerine 9 mass parts

1,3-butanediol 18 mass parts

Surfactant

^{* 1)}2 mass parts

2,2,4-trimethyl-1,3-pentanediol 2 mass parts

Proxel LV ^{* 2)}0.1 mass parts

Deionized water 18.9 mass parts

^*1) be expressed from the next:

C ₁₃H ₂₇-O-(CH ₂CH ₂O) ₈H

^*2) anticorrisive agent/antifungal agent, Avecia Co.

Ink mist recording adopts the mode similar to above-mentioned ink composite 1 to be prepared by above-mentioned ink composition with magenta ink (ink composite 9).

The preparation of ink composite 10

The composition of ink composite 10

Ink mist recording adopts the mode identical with ink composite 4 to prepare with magenta ink (ink composite 10), except the amount of glycerine increases to 13 mass parts by 9 mass parts, 1, the amount of 3-butanediol increases to 26 mass parts by 18 mass parts, and the amount of deionized water is reduced to 6.9 mass parts by 18.9 mass parts

Abrasive M-3 50 mass parts

Glycerine 13 mass parts

1,3-butanediol 26 mass parts

Surfactant

^{* 1)}2 mass parts

2,2,4-trimethyl-1,3-pentanediol 2 mass parts

Proxel LV ^{* 2)}0.1 mass parts

Deionized water 6.9 mass parts

^*1) be expressed from the next:

C ₁₃H ₂₇-O-(CH ₂CH ₂O) ₈H

^*2) anticorrisive agent/antifungal agent, Avecia Co.

The preparation of ink composite 11

The composition of ink composite 11

The composition of abrasive (M-6)

Solvent red 218 ^{* 1)}16 mass parts

Titanium dioxide fine particles ^{* 2)}4 mass parts

Polymer 3 16 mass parts

Deionized water 64 mass parts

^*1) oil-soluble magenta dye Oleosol Fast Pink FB, Taoka Chemical Co.

^*2)PT-401M，Ishihara?Sangyo?Kaisha?Ltd.

Abrasive (M-6) with 15 quality % dye strengths adopts the composition production of the mode similar to abrasive (C-1) by abrasive (M-6), except the processing time in kneader device becomes 20 minutes.

The dyestuff that obtains for containing of producing in abrasive and the polymer beads of inorganic pigment granules are measured the equal particle diameter of body; The results are shown in the table 1.This measurement is carried out with UPA 150 (Microtrac Co.).

Ink mist recording adopts with above-mentioned ink composite 4 similar modes with magenta ink (ink composite 11) and prepares, except the abrasive with ink composite 4 becomes abrasive (M-6).

The preparation of ink composite 12

The composition of ink composite 12

Ink composite 12 adopts with ink composite 5 similar modes and prepares, and except with the 3-methyl isophthalic acid, the 3-butanediol becomes 1, the 6-hexylene glycol.

The preparation of ink composite 13

Abrasive (M-7) 40 mass parts

Glycerine 12 mass parts

1,5-pentanediol 12 mass parts

3-methyl-2,4-heptandiol 2 mass parts

Softanol7025

^{* 1)}1 mass parts

Proxel LV ^{* 2)}0.1 mass parts

Deionized water 32.9 mass parts

^*1) surfactant, Nippon Shokubai Co.

^*2) anticorrisive agent/antifungal agent, Avecia Co.

To be dissolved in except that the mentioned component the abrasive (M-7) in the deionized water with the preparation carrier, this carrier will fully be mixed with abrasive (M-7),, thereby prepare the ink mist recording magenta ink then with the filter filtration of mixture usefulness average pore size 1 μ m.

The preparation of ink composite 14

Abrasive (M-8) 40 mass parts

Glycerine 24 mass parts

Softanol7025

^{* 1)}1 mass parts

Proxel LV ^{* 2)}0.1 mass parts

Deionized water 34.9 mass parts

^*1) surfactant, Nippon Shokubai Co.

^*2) anticorrisive agent/antifungal agent, Avecia Co.

Ink mist recording adopts the mode similar to above-mentioned ink composite 13 to be prepared by above-mentioned ink composition with magenta ink.

The preparation of ink composite 15

Abrasive (M-8) 40 mass parts

Glycerine 6 mass parts

Dipropylene glycol 18 mass parts

3-methyl-2,4-heptandiol 2 mass parts

Proxel LV ^{* 1)}0.1 mass parts

Deionized water 33.9 mass parts

^*1) anticorrisive agent/antifungal agent, Avecia Co.

The preparation of ink composite 16

Abrasive (K-1) 40 mass parts

Glycerine 6 mass parts

Triethylene glycol 18 mass parts

3-methyl-2,4-heptandiol 2 mass parts

FT-110 ^{* 1)}1 mass parts

Proxel LV ^{* 2)}0.1 mass parts

Deionized water 32.9 mass parts

^*1) fluorine-containing surfactant, Neos Company Ltd.

^*2) anticorrisive agent/antifungal agent, Avecia Co.

Inkjet recording black ink adopts the mode similar to above-mentioned ink composite 13 to be prepared by above-mentioned ink composition.

The preparation of ink composite 17

Abrasive (Y-1) 40 mass parts

Glycerine 6 mass parts

1,6-hexylene glycol 18 mass parts

2,2,4-trimethyl-1,3-pentanediol 2 mass parts

Softanol 7025 ^{* 1)}1 mass parts

Proxel LV ^{* 2)}0.1 mass parts

Deionized water 32.9 mass parts

^*1) surfactant, Nippon Shokubai Co.

^*2) anticorrisive agent/antifungal agent, Avecia Co.

Ink mist recording adopts the mode similar to above-mentioned ink composite 13 to be prepared by above-mentioned ink composition with Yellow ink.

The preparation of ink composite 18

Abrasive (Y-1) 40 mass parts

Glycerine 6 mass parts

1,3-butanediol 18 mass parts

3-methyl-2,4-heptandiol 2 mass parts

FT-110 ^{* 1)}1 mass parts

2-amino-2-methyl-1, ammediol 0.2 mass parts

Proxel LV ^{* 2)}0.1 mass parts

Deionized water 32.7 mass parts

^*1) fluorine-containing surfactant, Neos Company Ltd.

^*2) anticorrisive agent/antifungal agent, Avecia Co.

The preparation of ink composite 19

Abrasive (M-9) 40 mass parts

Glycerine 6 mass parts

Ethylene glycol monobutyl ether 18 mass parts

2,2,4-trimethyl-1,3-pentanediol 2 mass parts

FT-110 ^{* 1)}1 mass parts

2-amino-2-methyl-1, ammediol 0.2 mass parts

Proxel LV ^{* 2)}0.1 mass parts

Deionized water 32.7 mass parts

^*1) fluorine-containing surfactant, Neos Company Ltd.

^*2) anticorrisive agent/antifungal agent, Avecia Co.

The preparation of ink composite 20

Abrasive (M-9) 40 mass parts

Glycerine 6 mass parts

Propane diols 18 mass parts

3-methyl-2,4-heptandiol 2 mass parts

Surfinol465

^{* 1)}1 mass parts

Triethanolamine 0.2 mass parts

Proxel LV ^{* 2)}0.1 mass parts

Deionized water 32.7 mass parts

^*1) surfactant, Nissin Chemical Industry Co.

^*2) anticorrisive agent/antifungal agent, Avecia Co.

The preparation of ink composite 21

Abrasive (C-2) 40 mass parts

Glycerine 6 mass parts

N-N-methyl-2-2-pyrrolidone N-18 mass parts

2,2,4-trimethyl-1,3-pentanediol 2 mass parts

Surfinol465

^{* 1)}1 mass parts

Lithium hydroxide 0.2 mass parts

Proxel LV ^{* 2)}0.1 mass parts

Deionized water 32.7 mass parts

^*1) surfactant, Nissin Chemical Industry Co.

^*2) anticorrisive agent/antifungal agent, Avecia Co.

Ink mist recording adopts the mode similar to above-mentioned ink composite 13 to be prepared by above-mentioned ink composition with cyan ink.

The preparation of ink composite 22

Abrasive (C-3) 40 mass parts

Glycerine 6 mass parts

2-Pyrrolidone 18 mass parts

2,2,4-trimethyl-1,3-pentanediol 2 mass parts

Surfinol465

^{* 1)}1 mass parts

Triethanolamine 0.2 mass parts

Proxel LV ^{* 2)}0.1 mass parts

Deionized water 32.7 mass parts

^*1) surfactant, Nissin Chemical Industry Co.

^*2) anticorrisive agent/antifungal agent, Avecia Co.

The preparation of ink composite 23

Abrasive (C-3) 40 mass parts

Glycerine 6 mass parts

The 3-methyl isophthalic acid, 3-butanediol 18 mass parts

3-methyl-2,4-heptandiol 2 mass parts

FT-110 ^{* 1)}1 mass parts

2-amino-2-methyl-1, ammediol 0.2 mass parts

Proxel LV ^{* 2)}0.1 mass parts

Deionized water 32.7 mass parts

^*1) fluorine-containing surfactant, Neos Company Ltd.

^*2) anticorrisive agent/antifungal agent, Avecia Co.

The preparation of ink composite 24

Direct blue 199 ^{* 1)}6 mass parts

Glycerine 6 mass parts

N-N-methyl-2-2-pyrrolidone N-18 mass parts

3-methyl-2,4-heptandiol 2 mass parts

Surfinol 465 ^{* 2)}1 mass parts

2-amino-2-methyl-1, ammediol 0.2 mass parts

Proxel LV ^{* 3)}0.1 mass parts

Deionized water 66.7 mass parts

^*1) direct dyes Irgasperse Jet Cyan RL, Ciba Specialty Chemicals Inc.

^*2) surfactant, Nissin Chemical Industry Co.

^*3) anticorrisive agent/antifungal agent, Avecia Co.

To be dissolved in except that the mentioned component direct blue 199 in the deionized water with the preparation carrier, with this carrier with directly blue 199 mixes, then with the filter filtration of mixture, thereby prepare the ink mist recording cyan ink with average pore size 0.5 μ m.

The preparation of ink composite 25

Abrasive (M-7) 40 mass parts

1,5-pentanediol 24 mass parts

3-methyl-2,4-heptandiol 2 mass parts

Softanol7025

^{* 1)}1 mass parts

Proxel LV ^{* 2)}0.1 mass parts

Deionized water 32.9 mass parts

^*1) surfactant, Nippon Shokubai Co.

^*2) anticorrisive agent/antifungal agent, Avecia Co.

Ink mist recording adopts the mode identical with ink composite 13 to prepare with magenta ink, and except removing glycerine from the composition of ink composite 13, and with 1, the 5-pentanediol increases to 24 mass parts.

The preparation of ink composite 26

Abrasive (Y-1) 40 mass parts

1,6-hexylene glycol 24 mass parts

2,2,4-trimethyl-1,3-pentanediol 2 mass parts

Softanol7025

^{* 1)}1 mass parts

Proxel LV ^{* 2)}0.1 mass parts

Deionized water 32.9 mass parts

^*1) surfactant, Nippon Shokubai Co.

^*2) anticorrisive agent/antifungal agent, Avecia Co.

Ink mist recording adopts the mode similar with ink composite 13 to be prepared by the ink composition of ink composite 17 with Yellow ink, and except from wherein removing glycerine, and with 1, the 6-hexylene glycol increases to 24 mass parts.

The preparation of ink composite 27

Abrasive (C-4) 40 mass parts

Glycerine 6 mass parts

The 3-methyl isophthalic acid, 3-butanediol 18 mass parts

3-methyl-2,4-heptandiol 2 mass parts

FT-110 ^{* 1)}1 mass parts

2-amino-2-methyl-1, ammediol 0.2 mass parts

Proxel LV ^{* 2)}0.1 mass parts

Deionized water 32.7 mass parts

^*1) fluorine-containing surfactant, Neos Company Ltd.

^*2) anticorrisive agent/antifungal agent, Avecia Co.

Ink mist recording adopts the mode similar with ink composite 13 to be prepared by the ink composition of ink composite 23 with cyan ink, except abrasive (C-2) is become abrasive (C-4).

The equal particle diameter of body, viscosity, surface tension, pH and the dissolving content of the ink composite 1-27 that measures.The results are shown in the table 2.

(i) the equal particle diameter of body

The equal particle diameter of body adopts UPA-EX150 (Microtrac Co.) measuring with behind 500 times of the deionized water dilution testing samples under 25 ℃.

(ii) viscosity

Viscosity adopts RC-500 (Toki Sangyo Co.) to measure down at 25 ℃.

(iii) surface tension

Surface tension adopts Model CBVP-Z (Kyowa Interface Science Co.) to measure down at 25 ℃.

(iv)pH

PH adopts pH BOY-P2 (Shindengen Electric Mfg.Co.) to measure down at 25 ℃.

(v) dissolve content

The dissolving colorant can pass through the branch optical absorption spectra of the filtrate of employing spectrophotometer measurement ink composite and ink composite with respect to the ratio (%) of colorant in the printing ink, and relatively they are measured in the absorption at peak wavelength place.For separating discrete particles and dissolved material, filter method desirably is ultrafiltration.

Adopting molecular cut off is that the Biomax PXB050A50 (Millipore Co.) of 50,000 (corresponding to 5nm conversion particle diameters) is as ultrafiltration apparatus.Adopt U-3310 (Hitachi Co.) as the spectrum in the spectrophotometer measurement 200-800nm wave-length coverage.

Specifically, following measurement and calculating dissolving content.At first, distribute to measuring absorption spectrum as the printing ink of stoste.The concentration of printing ink is typically excessive in its stoste, therefore with pure water with this printing ink dilution 500-5,000 times (record thinner ratio Ka), and the printing ink of dilution inserted in the spectrophotometric measuring cell.Pure water is packed in the reference cell, and in the visible-range of 340-800nm, described pond is scanned at least, to obtain the branch optical absorption spectra of the stoste shown in the symbol ■ among Fig. 7 with 5nm or littler sampling interval.After measuring the branch optical absorption spectra printing ink stoste is handled with ultrafiltration.Filtrate is diluted to available Spectrophotometric concentration, record thinner ratio Kb, the filtrate of dilution is inserted in the spectrophotometric measuring cell, under the condition identical, measure, thereby obtain the branch optical absorption spectra of the filtrate shown in the symbol △ among Fig. 7 with printing ink stoste.Obtain value A, the B of absorbance (abs) at the absworption peak wavelength place of stoste and filtrate, calculate dissolving content by following equation then.When having two or more peak, preferably select maximum peak for absorbance (abs).

Dissolving content (%)=(Kb * B)/(Ka * A) * 100

Dissolving content among Fig. 7 can for example following calculating.

Dissolving content (%)=(90 * 2.24)/(2000 * 1.74) * 100=5.8%

Table 2

Measure the pure water transfer amount of following seven kinds of recording mediums that are used to assess.The results are shown in table 3.Measure and adopt dynamic scan absorptiometer (K350 series D type, Kyowaseiko Co.) to carry out.

Recording medium

Recording medium A: aurora coating, basic weight=104.7g/m ²(Nippon Paper Industries Co.), base material: paper pulp, coating: kaolin, calcium carbonate, starch and adhesive resin (two-sided), thickness: about 100 μ m;

Recording medium B:POD gloss coating 100g/m ²Paper (Oji Paper Co.);

Recording medium C: hyperfine dedicated paper (Seiko Epson Co.);

Recording medium C ': hyperfine paper (Seiko Epson Co.), base material: paper pulp, coating: silica, aluminium oxide, starch and adhesive resin (single face), thickness: about 120 μ m;

Recording medium D:Lumirror U10 (Toray Industries Inc.);

Recording medium D ': Lumirror U12 (Toray Industries Inc.), base material: polyester (PET) film, coating: do not have thickness: about 125 μ m;

Recording medium E:Space DX unglazed finish, ink-jet is with unglazed coated paper (Nippon PaperIndustries Co.), base material: paper pulp, coating: kaolin, calcium carbonate, starch and adhesive resin (two-sided), thickness: about 60 μ m;

Table 3

Quantity of ink (the ml/m that in five kinds of recording mediums, shifts ²) measurement result be shown in following table 4 and 5.Measure and adopt dynamic scan absorptiometer (K350 series D type, Kyowaseiko Co.) to carry out.

Table 4

Table 5

Ink recorded matter with Ipsio G7570 (Ricoh Co.) by the printing ink that obtains and above-mentioned seven kinds of recording medium productions.The project of evaluate image quality and assessment result thereof are shown among the table 6-10.

(i) diffusion

Four point character according to following standard visual assessment printing image.

A: clear, and do not have ink diffusion

B: slightly fuzzy, can the permission level but be in

C: diffusion

D: diffusion makes character be difficult to identification

(ii) print through (strike through)

Adopt reflection/color dispersing densitometer (X-Rite Co.) from partly back side measurement image density on the spot.From this measured value, deduct the measured value of the image density of recording medium itself, obtain the print through density value, and according to following criterion evaluation.Admissible level is to be lower than 0.10 print through density.

A: print through density (STD)＜0.05

B：0.05≤STD<0.10

C：0.10≤STD<0.20

D：0.20≤STD

(iii) Cheng Zhu (sparing property of density unevenness)

The uneven level of partial density is according to following standard visual assessment on the spot.

A: fully evenly, it is even to discover density unevenness

B: discernable density unevenness is even, can the permission level but be in

C: the discernable density unevenness of level that can not allow is even

D: significantly density unevenness is even

(iv) color saturation

Calculate the color saturation of the coloured image that adopts reflection/color dispersing densitometer (X-Rite Co.) measurement and the color saturation (yellow: 91.34, magenta: 74.55, cyan: 62.82 of Standard Colors, Japan colorver.2) ratio, and assess according to following standard.Admissible level is B or better.

A:1.0≤ratio

B:0.8≤ratio＜1.0

C:0.7≤ratio＜0.8

D: ratio＜0.7

(v) promoters stain

Because of partly giving prominence to the level of the anti-seal pollution that causes according to following standard visual assessment on the spot to background parts.Admissible level is 3 or better.

3 grades: not anti-seal pollutes

2 grades: slight anti-seal pollutes

1 grade: obviously anti-seal pollutes

Table 6 recording medium A

	Diffusion	Print through	Cheng Zhu	Color saturation	The promoters stain
	Diffusion	Print through	Cheng Zhu	Color saturation	The promoters stain	Printing ink 1	B	A	B	A	3
Printing ink 2	B	B	A	A		Printing ink 1	B	A	B	A	3	3
Printing ink 2	B	B	A	A		Printing ink 3	B	A	A	A	3	3
Printing ink 4	B	B	A	A		Printing ink 3	B	A	A	A	3	3
Printing ink 4	B	B	A	A		Printing ink 5	B	A	A	A	3	3
Printing ink 6	C	A	D	B		Printing ink 5	B	A	A	A	3	2
Printing ink 6	C	A	D	B		Printing ink 7	D	D	D	D	2	2
Printing ink 8	D	C	C	C		Printing ink 7	D	D	D	D	2	2
Printing ink 8	D	C	C	C		Printing ink 9	B	A	D	B	2	2
Printing ink 10	B	B	B	B		Printing ink 9	B	A	D	B	2	3
Printing ink 10	B	B	B	B		Printing ink 11	B	A	B	B	3	3
Printing ink 12	B	B	A	A		Printing ink 11	B	A	B	B	3	3
Printing ink 12	B	B	A	A		Printing ink 13	C	B	C	B	3	3
Printing ink 14	C	B	B	B		Printing ink 13	C	B	C	B	3	2
Printing ink 14	C	B	B	B		Printing ink 15	B	A	C	B	3	2
Printing ink 16	B	A	A	-	2	Printing ink 15	B	A	C	B	3
Printing ink 16	B	A	A	-	2	Printing ink 17	B	A	A	A	2
Printing ink 18	B	A	B	A		Printing ink 17	B	A	A	A	2	2
Printing ink 18	B	A	B	A		Printing ink 19	C	B	B	B	3	2
Printing ink 20	C	A	A	A		Printing ink 19	C	B	B	B	3	3
Printing ink 20	C	A	A	A		Printing ink 21	B	A	A	A	3	3
Printing ink 22	B	A	A	A		Printing ink 21	B	A	A	A	3	3
Printing ink 22	B	A	A	A		Printing ink 23	B	A	B	A	3	3
Printing ink 24	D	D	B	D		Printing ink 23	B	A	B	A	3	2
Printing ink 24	D	D	B	D		Printing ink 25	D	C	B	B	2	2
Printing ink 26	D	B	B	A		Printing ink 25	D	C	B	B	2	2
Printing ink 26	D	B	B	A		Printing ink 27	B	A	C	B	2	2

Table 7 recording medium B

	Diffusion	Print through	Cheng Zhu	Color saturation	The promoters stain
	Diffusion	Print through	Cheng Zhu	Color saturation	The promoters stain	Printing ink 1	B	B	A	A	3
Printing ink 2	B	B	A	A		Printing ink 1	B	B	A	A	3	3
Printing ink 2	B	B	A	A		Printing ink 3	A	A	A	A	3	3
Printing ink 4	B	B	A	A		Printing ink 3	A	A	A	A	3	3
Printing ink 4	B	B	A	A		Printing ink 5	B	A	A	A	3	3
Printing ink 6	C	A	D	C		Printing ink 5	B	A	A	A	3	2
Printing ink 6	C	A	D	C		Printing ink 7	D	D	C	D	2	2
Printing ink 8	C	B	D	C		Printing ink 7	D	D	C	D	2	2
Printing ink 8	C	B	D	C		Printing ink 9	A	A	D	B	2	2
Printing ink 10	B	B	B	B		Printing ink 9	A	A	D	B	2	3
Printing ink 10	B	B	B	B		Printing ink 11	B	A	A	A	3	3
Printing ink 12	B	B	A	A		Printing ink 11	B	A	A	A	3	3
Printing ink 12	B	B	A	A		Printing ink 13	B	A	B	B	2	3
Printing ink 14	B	B	A	B		Printing ink 13	B	A	B	B	2	2
Printing ink 14	B	B	A	B		Printing ink 15	A	A	A	B	2	2
Printing ink 16	A	A	A	-	2	Printing ink 15	A	A	A	B	2
Printing ink 16	A	A	A	-	2	Printing ink 17	A	B	A	B	2
Printing ink 18	A	A	A	B		Printing ink 17	A	B	A	B	2	2
Printing ink 18	A	A	A	B		Printing ink 19	B	A	B	A	3	2
Printing ink 20	B	A	A	A		Printing ink 19	B	A	B	A	3	3
Printing ink 20	B	A	A	A		Printing ink 21	A	A	A	A	3	3
Printing ink 22	A	A	A	A		Printing ink 21	A	A	A	A	3	3
Printing ink 22	A	A	A	A		Printing ink 23	A	A	A	A	3	3
Printing ink 24	D	D	A	D		Printing ink 23	A	A	A	A	3	2
Printing ink 24	D	D	A	D		Printing ink 25	D	D	B	B	2	2
Printing ink 26	C	C	A	B		Printing ink 25	D	D	B	B	2	2
Printing ink 26	C	C	A	B		Printing ink 27	A	A	B	C	2	2

Table 8 recording medium C

	Diffusion	Print through	Cheng Zhu	Color saturation	The promoters stain
	Diffusion	Print through	Cheng Zhu	Color saturation	The promoters stain	Printing ink 1	C	A	A	A	3
Printing ink 2	C	A	A	A		Printing ink 1	C	A	A	A	3	3
Printing ink 2	C	A	A	A		Printing ink 3	C	A	A	A	3	3
Printing ink 4	? C	? A	? A	? A	? 3	Printing ink 3	C	A	A	A	3
Printing ink 4	? C	? A	? A	? A	? 3	Printing ink 5	C	A	A	A	3
Printing ink 6	C	A	B	B		Printing ink 5	C	A	A	A	3	2
Printing ink 6	C	A	B	B		Printing ink 7	C	A	B	A	3	2
Printing ink 8	C	A	A	A		Printing ink 7	C	A	B	A	3	3
Printing ink 8	C	A	A	A		Printing ink 9	C	A	A	B	3	3
Printing ink 10	C	A	B	B		Printing ink 9	C	A	A	B	3	3
Printing ink 10	C	A	B	B		Printing ink 11	C	A	A	B	3	3
Printing ink 12	C	A	A	A		Printing ink 11	C	A	A	B	3	3
Printing ink 12	C	A	A	A		Printing ink 13	A	A	A	A	2	3
Printing ink 14	A	A	A	B		Printing ink 13	A	A	A	A	2	2
Printing ink 14	A	A	A	B		Printing ink 15	A	A	A	C	2	2
Printing ink 16	A	A	A	-	2	Printing ink 15	A	A	A	C	2
Printing ink 16	A	A	A	-	2	Printing ink 17	A	A	A	A	2
Printing ink 18	A	A	A	C		Printing ink 17	A	A	A	A	2	2
Printing ink 18	A	A	A	C		Printing ink 19	B	A	A	A	2	2
Printing ink 20	A	A	A	A		Printing ink 19	B	A	A	A	2	2
Printing ink 20	A	A	A	A		Printing ink 21	A	A	A	A	2 2	2
Printing ink 22	A	A	A	A		Printing ink 21	A	A	A	A	2 2	2
Printing ink 22	A	A	A	A		Printing ink 23	A	A	A	A	2	2
Printing ink 24	B	A	A	B		Printing ink 23	A	A	A	A	2	2
Printing ink 24	B	A	A	B		Printing ink 25	C	A	A	A	2	2
Printing ink 26	C	A	A	A		Printing ink 25	C	A	A	A	2	2
Printing ink 26	C	A	A	A		Printing ink 27	C	A	A	B	3	2

Table 9 recording medium D/D '

	Diffusion	Print through	Cheng Zhu	Color saturation	The promoters stain
	Diffusion	Print through	Cheng Zhu	Color saturation	The promoters stain	Printing ink 1	B	A	D	D	1
Printing ink 2	C	A	D	C		Printing ink 1	B	A	D	D	1	1
Printing ink 2	C	A	D	C		Printing ink 3	B	A	D	C	1	1
Printing ink 4	B	A	D	C		Printing ink 3	B	A	D	C	1	1
Printing ink 4	B	A	D	C		Printing ink 5	B	A	D	C	1	1
Printing ink 6	? D	? A	? D	? D	? 1	Printing ink 5	B	A	D	C	1
Printing ink 6	? D	? A	? D	? D	? 1	Printing ink 7	D	A	D	D	1
Printing ink 8	D	A	D	D		Printing ink 7	D	A	D	D	1	1
Printing ink 8	D	A	D	D		Printing ink 9	B	A	D	C	1	1
Printing ink 10	C	A	D	B		Printing ink 9	B	A	D	C	1	1
Printing ink 10	C	A	D	B		Printing ink 11	B	A	D	B	2	1
Printing ink 12	C	A	D	A		Printing ink 11	B	A	D	B	2	2
Printing ink 12	C	A	D	A		Printing ink 13	A	A	D	C	1	2
Printing ink 14	A	A	D	D		Printing ink 13	A	A	D	C	1	1
Printing ink 14	A	A	D	D		Printing ink 15	A	A	D	C	1	1
Printing ink 16	A	A	D	-	1	Printing ink 15	A	A	D	C	1
Printing ink 16	A	A	D	-	1	Printing ink 17	A	A	D	C	1
Printing ink 18	A	A	D	C		Printing ink 17	A	A	D	C	1	1
Printing ink 18	A	A	D	C		Printing ink 19	A	A	D	C	1	1
Printing ink 20	A	A	D	C		Printing ink 19	A	A	D	C	1	1
Printing ink 20	A	A	D	C		Printing ink 21	A	A	D	C	1	1
Printing ink 22	A	A	D	C		Printing ink 21	A	A	D	C	1	1
Printing ink 22	A	A	D	C		Printing ink 23	A	A	D	C	1	1
Printing ink 24	D	A	D	D		Printing ink 23	A	A	D	C	1	1
Printing ink 24	D	A	D	D		Printing ink 25	D	A	D	C	1	1
Printing ink 26	D	A	D	C		Printing ink 25	D	A	D	C	1	1
Printing ink 26	D	A	D	C		Printing ink 27	C	A	D	D	1	1

Table 10 recording medium E

	Diffusion	Print through	Cheng Zhu	Color saturation	The promoters stain
	Diffusion	Print through	Cheng Zhu	Color saturation	The promoters stain	Printing ink 1	B	A	A	A	3
Printing ink 2	B	B	A	A		Printing ink 1	B	A	A	A	3	3
Printing ink 2	B	B	A	A		Printing ink 3	B	A	A	A	3	3
Printing ink 4	B	A	A	A		Printing ink 3	B	A	A	A	3	3
Printing ink 4	B	A	A	A		Printing ink 5	B	A	A	A	3	3
Printing ink 6	C	A	D	B		Printing ink 5	B	A	A	A	3	2
Printing ink 6	C	A	D	B		Printing ink 7	D	C	A	C	3 3	2
Printing ink 8	C	C	C	B		Printing ink 7	D	C	A	C	3 3	3
Printing ink 8	C	C	C	B		Printing ink 9	A	A	D	B	2	3
Printing ink 10	B	B	A	B		Printing ink 9	A	A	D	B	2	3
Printing ink 10	B	B	A	B		Printing ink 11	B	A	A	A	3	3
Printing ink 12	B	B	A	A		Printing ink 11	B	A	A	A	3	3
Printing ink 12	B	B	A	A		Printing ink 13	B	B	B	B	2	3
Printing ink 14	B	A	A	B		Printing ink 13	B	B	B	B	2	2
Printing ink 14	B	A	A	B		Printing ink 15	A	A	B	B	2 2	2
Printing ink 16	A	A	A	-	2	Printing ink 15	A	A	B	B	2 2
Printing ink 16	A	A	A	-	2	Printing ink 17	A	A	A	B	2
Printing ink 18	A	A	A	A		Printing ink 17	A	A	A	B	2	2
Printing ink 18	A	A	A	A		Printing ink 19	B	A	A	A	3	2
Printing ink 20	B	A	A	A		Printing ink 19	B	A	A	A	3	3
Printing ink 20	B	A	A	A		Printing ink 21	A	A	A	A	3	3
Printing ink 22	A	A	A	A		Printing ink 21	A	A	A	A	3	3
Printing ink 22	A	A	A	A		Printing ink 23	A	A	A	A	3	3
Printing ink 24	D	D	A	D		Printing ink 23	A	A	A	A	3	2
Printing ink 24	D	D	A	D		Printing ink 25	D	C	B	B	2	2
Printing ink 26	C	B	A	A		Printing ink 25	D	C	B	B	2	2
Printing ink 26	C	B	A	A		Printing ink 27	A	A	A	C	3	2

Recording medium C ', D ' and C, D are equal to, and assessment result is also identical.

Industrial applicibility

Can have the absorbefacient recording medium of particular liquid by combination according to printing ink-media pack of the present invention provides highly meticulous, high-quality image with the ink composite with particular surface tension force, thereby can be advantageously used in print cartridge, ink recorded matter, ink-jet recording apparatus and ink jet recording method.

Can be used in the record of multiple ink jet recording method according to ink-jet recording apparatus of the present invention and ink jet recording method, also be particularly advantageous for ink mist recording printer, facsimile machine, duplicator and printer/facsimile machine/duplicator set composite.

Claims

1. a printing ink-media pack comprises ink composite and recording medium,

Wherein said ink composite comprises polymer particles, water-soluble solvent, He Shui, and has the surface tension of 20mN/m to 35mN/m under 25 ℃, and this polymer particles contains dyestuff and inorganic pigment granules, and

Described recording medium comprises support and the coating on the one side at least of this support, measures by the dynamic scan absorptiometer, and the pure water amount that shifts to this recording medium is not less than 2ml/m time of contact at 100ms ²And less than 35ml/m ², be not less than 3ml/m time of contact at 400ms ²And less than 40ml/m ²

2. according to the printing ink-media pack of claim 1, the viscosity of wherein said ink composite is 5mPa.s to 50mPas down at 25 ℃.

3. according to the printing ink-media pack of claim 1 or 2, wherein said dyestuff is at least a in oil-soluble dyes and the disperse dyes.

4. according to each printing ink-media pack in the claim 1 to 3, wherein said inorganic pigment granules is a kind of in titanium dioxide granule, alumina particle and the silica dioxide granule.

5. according to each printing ink-media pack in the claim 1 to 4, wherein contain polymer in the polymer particles of dyestuff and inorganic pigment microparticles and be at least a in mylar, polyurethane resin, vinylite and the acrylic resin.

6. according to each printing ink-media pack in the claim 1 to 5, the equal particle diameter of body that wherein contains the polymer particles of dyestuff and inorganic pigment microparticles is 5nm to 200nm.

7. according to each printing ink-media pack in the claim 1 to 6, wherein said water-soluble solvent is glycerine, diethylene glycol (DEG), triethylene glycol, 1,3-butanediol, 1,6-hexylene glycol, propane diols, 1,5-pentanediol, dipropylene glycol, trimethylolpropane and 3-methyl isophthalic acid, at least a in the 3-butanediol.

8. according to each printing ink-media pack in the claim 1 to 7, wherein said printing ink-media pack comprises at least a in polyol compound with 8 or more carbon atoms and the glycol ethers compound.

9. according to the printing ink-media pack of claim 1, wherein on described recording medium the described ink composite of deposition printing,

Described ink composite comprises organic solvent, water and colouring agent, and described colouring agent is water insoluble substantially and be dissolved in described organic solvent,

Described colouring agent exists with dispersity and dissolved state in water and described organic solvent, by molecular cut off is 50, after 000 ultrafiltration separates, the amount of colouring agent that is in dissolved state based on the total amount of colouring agent in the ink composite for being not more than 10%, and

Measure by the dynamic scan absorptiometer, the amount of this ink composite that shifts to this recording medium is 4ml/m in 100ms time of contact ²To 15ml/m ², be 7ml/m in 400ms time of contact ²To 20ml/m ²

10. an ink composite comprises organic solvent, water and colouring agent,

Wherein said colouring agent is water insoluble substantially and be dissolved in described organic solvent,

This ink composite is used for according to＜1〉to＜9〉each printing ink-media pack.

11. a print cartridge comprises in container according to the ink composite in each printing ink-media pack in the claim 1 to 9.

12. ink jet recording method, at least comprise the ink jet step, wherein in this ink jet step, to applying stimulation, with by spraying this ink composite document image on the recording medium of this printing ink-media pack according to the ink composite in each printing ink-media pack in the claim 1 to 9.

13. ink-jet recording apparatus, at least comprise the ink jet unit, wherein by this ink jet unit to applying stimulation, with by spraying this ink composite document image on the recording medium of this printing ink-media pack according to the ink composite in each printing ink-media pack in the claim 1 to 9.

14. an ink recorded matter is included in the image that forms according to the ink composite that uses this printing ink-media pack on the recording medium in each printing ink-media pack in the claim 1 to 9.