CN101096479A - Recording ink as well as ink media set, ink cartridge, ink recorded matter, inkjet recording apparatus and inkjet recording method - Google Patents

Recording ink as well as ink media set, ink cartridge, ink recorded matter, inkjet recording apparatus and inkjet recording method Download PDF

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Publication number
CN101096479A
CN101096479A CN 200710137903 CN200710137903A CN101096479A CN 101096479 A CN101096479 A CN 101096479A CN 200710137903 CN200710137903 CN 200710137903 CN 200710137903 A CN200710137903 A CN 200710137903A CN 101096479 A CN101096479 A CN 101096479A
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China
Prior art keywords
ink
mentioned
recording
quality
water
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CN 200710137903
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Inventor
有贺保
小谷野正行
松山彰彦
羽桥尚史
后藤宽
大嶋享
诸星直哉
永井希世文
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Ricoh Co Ltd
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Ricoh Co Ltd
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Abstract

A recording ink containing at least a solid component which contains a colorant and a resin and is a solid at 25 DEG C, a liquid component which has a higher boiling point than that of water and is a liquid at 25 DEG C and water, wherein the total content of the liquid component in the recording ink is 20% by mass or less, the total content of the solid component in the recording ink is 20% by mass or more, and the total content of a resin component in the solid component is 40% by mass to 95% by mass relative to a total amount of the solid component is provided.

Description

Recording ink and ink medium group, print cartridge, ink recorded matter, ink-jet recording device and ink jet recording method
Technical field
The ink medium group (ink media set), print cartridge, ink recorded matter, ink-jet recording device and the ink jet recording method that the present invention relates to be suitable for the recording ink of ink-vapor recording and use this recording ink.
Background technology
Ink jet recording method is the small droplets flight that makes printing ink, and adheres on the recording medium such as paper and carry out method of printing.As the printing ink that in this ink jet recording method, uses, generally the tinting material of various dyestuffs or pigment is dissolved or dispersed in water or water and the high boiling organic solvent, contains the printing ink that is useful on the wetting agent that comprises high boiling organic solvent of keeping moisture retention in addition in a large number.This wetting agent that comprises high boiling organic solvent helps to prevent the drying of nozzle owing to its water retention capacity.But when at the fast paper of wetting-out rate, when for example printing on common paper, wetting agent is difficult to evaporation, thereby exists print through to become many shortcomings.
On the other hand, the little paper of water-retaining capacities such as non-porous base material such as the hectograph White Board (offset coated paper) of printing usefulness or plastic film, plastic layer platen, plastic coated paper are difficult to evaporate wetting agent, therefore, need cost plenty of time drying, thus and it is impracticable.
Therefore, even expectation provides a kind of drying such as printing of utilizing also rapid, image color is also high, even utilize common paper picture quality also high, even and the ink jet recording method of spray nozzle clogging also can not take place when stopping using for a long time.
For example, open the jetted ink that has proposed very little to contain wetting agent in the 2004-115551 communique the spy.According to this scheme, even use common paper also can obtain not have the picture quality of the high image density of print through.But this scheme does not contain resin in printing ink, and therefore, especially when using pigment ink, the fixation performance of image is poor.In addition, the raising of the rate of drying during about printing on the hectograph White Board, both not open, do not hint yet.
In addition, open the dye ink that has proposed rapid-drying properties in the clear 60-34992 communique the spy.But, in the embodiment of this scheme, contain a large amount of wetting agents, reach more than the 15 quality %, do not add resin, paper has used vellum, and the coated paper for printing that does not use very difficult suction is as object.
In addition, open the spy and proposed the rapid-drying properties printing ink relevant in the flat 8-109343 communique with the ink-jet of electrothermal method.But, do not add resin in this scheme yet, contain more ionogen, the fixation performance of image is poor, in addition, has adopted the different flying method of ink-jet essence with the piezoelectricity mode.
In addition, open the combination that has proposed microcapsule-type pigment and printing in 2002-67473 communique and the Te Kai 2002-69346 communique the spy.But these schemes are that common printing ink is formed, and therefore need utilize microwave to heat in order to improve drying property.
In addition, open the printing ink that has proposed to contain wax particulate and resin particle in the 2002-301857 communique the spy.According to the viewpoint that can give its wettability, use the wax particulate to substitute wetting agent in this scheme.But, above-mentioned wax with wettability photographic fixing or dry aspect relatively poor.
In addition, the spy opens the printing ink that flat 6-171072 communique has proposed to contain resin emulsion, macromolecule dispersing agent and pigment.The content of the printing ink wetting agent of this scheme is few, and still, because solid component concentration is little, existence can not obtain the enough image colors or the problem of colour developing.
In addition, open the spy that to have put down in writing a kind of viscosity in the 2003-226827 communique be printing ink more than the 5mPas, wherein contain fluorine class tensio-active agent and in polymer particles, contain water-insoluble or slightly water-soluble colorant and the polymer emulsion that forms.But, be not documented in the situation of the enterprising line items of non-porous medium such as plastic film.
In addition, when printing on non-water-absorbent recording mediums such as polyester film, in general common printing ink fixation performance, drying property are poor, therefore, use the printing ink (opening the 2000-117960 communique with reference to the spy) of ultraviolet hardening.But, need strong UV-light, and, be not general requirement for printer because of the keeping quality of printing ink maximizes device.
On the other hand,, improve the method for drying property and fixation performance in addition, but, therefore,, generally can not use in the place of disagreeable organic solvent smells such as office because solvent is an organic solvent for oil-based ink.
In addition, as the water color ink that on polyolefin film, prints, for example, the printing ink that high density ground contains resin in opening flat 4-139271 communique etc., the spy has been proposed.But record can be as the content of jetted ink purposes use.
In addition, open the spy and proposed polyvinyl chloride (PVC) RESINS sheet non-aqueous ink-jet inks in the 2005-15672 communique.This scheme is a non-aqueous inks, considers from environment aspects such as foul smell, and is not suitable for office.
In addition, as the jetted ink that on non-porous base materials such as vinyl medium, prints, there is the spy to open the printing ink of 2005-220352 communique record.Only according to embodiment, the solid substance total concn is 6 quality %, and wetting agent is 21 quality %.Has a low solid substance amount when this, moistening dosage is many, and the lower printing ink of viscosity printing ink adhesive capacity on unit surface especially causes the such liquid-flow of foaming (beading), for a long time easily by liquid (liquid bias) uneven problem of image color of causing partially on the image (solid image) on the spot.
In addition, open the spy and proposed the jetted ink that prints in the 2000-44858 communique on the vinyl medium, embodiment is to carry out drying under 70 ℃.In addition, with regard to embodiment, the moistening dosage in the printing ink is many, and the solid substance amount is lower than 10 quality %, therefore, must infer: dry just very slow if do not carry out heat drying, can not obtain clean image.Promptly, the solid substance amount of driving " the printing ink test portion 1 " put down in writing in the 2000-44858 communique above-mentioned spy is 11 quality % as calculated, though surpassed 10 quality %, resin contains polymer dispersant, be not emulsion-type, thereby can infer and to add a large amount of resins.
Therefore, present situation is, can obtain high image density when on common paper, printing, back side concentration is low, develop the color, the image that does not have stain, even and for printing or plastic film level and smooth and that water-retaining capacity is little, the plastic layer platen, non-porous base material such as plastic coated paper, rate of drying is also no problem, can obtain bright-coloured and approach the record images printing ink of print, with utilize this recording ink, even the ink jet recording method of spray nozzle clogging etc. also can not take place when stopping using for a long time, also do not provide to have the technology that can fully satisfy desired performance.
Summary of the invention
The object of the invention is, be provided at and also can obtain high image density when printing on the common paper, back side concentration is low, color developing good, the do not have bleeding image of (bleeding), in addition, even on level and smooth and printing that water-retaining capacity is little, print, rate of drying is also no problem, can obtain distinctness and approach the record images printing ink of print, even and adopted ink medium group, print cartridge, the ink recorded matter of this recording ink that the ink-jet recording device and the ink jet recording method of spray nozzle clogging also can not take place when stopping for a long time.
In addition, the invention provides can be at enterprising line items such as common paper and ink-jet dedicated papers, in addition, ink medium group, print cartridge, ink recorded matter, ink-jet recording device and the ink jet recording method of not selecting recording medium that can also on the low non-porous base material of water-retaining capacities such as plastic sheets such as polyester chips, plastic layer platen, plastic coated paper, glass, metal, write down well.
Recording ink of the present invention comprises at least and contains tinting material and resin and be that solid solids component, boiling point are higher and be the liquid component and the water of liquid under 25 ℃ than water under 25 ℃, the total content of aforesaid liquid composition in above-mentioned recording ink is below the 20 quality %, the total content of above-mentioned solids component in above-mentioned recording ink is more than the 20 quality %, and the total content of the resinous principle in this solids component is 40～95 quality % with respect to above-mentioned solids component total amount.
In recording ink of the present invention, the total content of the resinous principle in the above-mentioned solids component is 40～95 quality % with respect to the total amount of above-mentioned solids component, thereby make the fixation performance of tinting material and glossiness improve, when especially on common paper, printing, can obtain high image density, back side concentration is low, color developing the is good image that does not have bleeding.In addition, because the total content of aforesaid liquid composition in above-mentioned recording ink is below the 20 quality %, can shorten the time of drying of printing ink, when on the low level and smooth printing of water-retaining capacity, printing, also can improve rate of drying, obtain distinctness and have the image that approaches print glossy excellence.In addition, because the total content of above-mentioned solids component in above-mentioned recording ink be more than the 20 quality %, even the printing that is difficult to absorb water also can reach rapidly dry, even common paper also can obtain the image of the few high tone of print through.
In the 1st embodiment, ink medium group of the present invention comprises recording ink and recording medium;
Above-mentioned recording ink comprises at least and contains tinting material and resin and be that solid solids component, boiling point are higher and be the liquid component and the water of liquid than water under 25 ℃ that the total content of this liquid component in above-mentioned recording ink is below the 20 quality % under 25 ℃;
Above-mentioned recording medium has support and have the recording medium of coating layer on the one side at least of this support, and utilizing the dynamic scan imbibition instrumentation pure water of fixed duration of contact under the 100ms is 2～35ml/m to the transfer amount of above-mentioned recording medium 2, and the pure water under the duration of contact 400ms is 3～40ml/m to the transfer amount of above-mentioned recording medium 2
In the ink medium group that the 1st embodiment of the present invention relates to, higher and be the recording ink that the liquid component of liquid lacks under 25 ℃ by the little recording medium of combination water-retaining capacity and boiling point than water, can write down fast drying, have reflecting feel, and the image that blistered homogeneity is high is not found at the position on the spot.
At this moment, in the ink medium group that above-mentioned the 1st embodiment relates to, the total content of the solids component in the recording ink is more than the 20 quality %, and the content of the resinous principle in the solids component is that the such important document of 40～95 quality % has auxiliary effect to fixation performance and drying property, but might not be prerequisite, if it is below the 20 quality % that aforesaid liquid becomes component, even then use the low recording medium of the such water-retaining capacity of the recording medium of above-mentioned record, also can seek the raising of drying property.
In the 2nd embodiment, ink medium group of the present invention comprises recording ink and recording medium;
Above-mentioned recording ink comprises at least and contains tinting material and resin and be that solid solids component, boiling point are higher and be the liquid component and the water of liquid under 25 ℃ than water under 25 ℃;
The total content of aforesaid liquid composition in above-mentioned recording ink is below the 30 quality %;
The total content of above-mentioned solids component in above-mentioned recording ink is more than the 20 quality %, and the total content of the resinous principle in this solids component is 40～95 quality % with respect to above-mentioned solids component total amount;
Above-mentioned recording medium has support and the coating layer on the one side at least of this support, and utilizing the dynamic scan imbibition instrumentation pure water of fixed duration of contact under the 100ms is 2～35ml/m to the transfer amount of above-mentioned recording medium 2, and the pure water under the duration of contact 400ms is 3～40ml/m to the transfer amount of above-mentioned recording medium 2
In the ink medium group that the 2nd embodiment of the present invention relates to, by the transfer amount that makes up above-mentioned recording ink of the present invention and pure water is the recording medium of specialized range, can write down and have reflecting feel, and the image that blistered homogeneity is high is not found at the position on the spot.
In the 3rd embodiment, ink medium group of the present invention comprises recording ink and recording medium;
Above-mentioned recording ink comprises at least and contains tinting material and resin and be that solid solids component, boiling point are higher and be the liquid component and the water of liquid under 25 ℃ than water under 25 ℃;
The total content of aforesaid liquid composition in above-mentioned recording ink is below the 30 quality %;
Above-mentioned recording medium is made of non-porous base material.
In the ink medium group that the 3rd mode of the present invention relates to, by the tinting material in the raising recording ink and the solid component content of water-dispersed resin, improve resin ratio, further reduce surface tension, can improve at plastic sheets such as polyester chipss, the plastic layer platen, plastic coated paper, glass, wettability when printing on the low non-porous base material of water-retaining capacities such as metal, drying property, fixation performance, and, by reducing moistening dosage as best one can, can utilize water color ink at the enterprising line item of above-mentioned plastic film, and need not special devices such as well heater, do not need to use ultraviolet curing ink or oil-based ink yet.But dry in order to carry out high speed, it is favourable heating.
In addition, when as the containing ratio and be not less than above-mentioned scope of the wetting agent of liquid component (20 quality %～30 quality %), can not reach the sort of rapid-drying properties, therefore heating has effect for rapid-drying properties, but, owing to have high viscosity under high solid concentration, therefore, image color deviations such as air blister defect are compared still less with low viscosity, low solid concentration printing ink.On the other hand, when few to 20 quality % when following as the content of the wetting agent of liquid component, viscosity is lower, but because wetting agent is few, and the moisture evaporation in the printing ink is fast, and drying property is fast, and tackify is fast, and it is few that liquid flows this image deflects, and, can also be dry at a high speed.If moistening dosage is below the 10 quality %, then can reach rapid-drying properties faster.
In the 4th embodiment, ink medium group of the present invention comprises recording ink and recording medium;
Above-mentioned recording ink contains the colorant that contains water-insoluble or slightly water-soluble in polymer particles and pigment, water-dispersed resin particulate and the wetting agent of the polymer emulsion type that forms at least, the total solid amount of the pigment of above-mentioned polymer emulsion type and above-mentioned water-dispersed resin particulate is more than the 20 quality %, and the content of above-mentioned wetting agent is more than the 20 quality %;
It is 2～35ml/m to the transfer amount of above-mentioned recording medium that above-mentioned recording medium utilizes the dynamic scan imbibition instrumentation pure water of fixed duration of contact under the 100ms 2, and the pure water under the duration of contact 400ms is 3～40ml/m to the transfer amount of above-mentioned recording medium 2
In the 5th embodiment, ink medium group of the present invention comprises recording ink and recording medium;
Above-mentioned recording ink contains tinting material, water-dispersed resin particulate and wetting agent at least, the total content of the solid substance in this recording ink is more than the 20 quality %, the content of above-mentioned wetting agent is more than the 20 quality %, this wetting agent is independent glycerine, and perhaps the content of glycerine in above-mentioned wetting agent is more than the 80 quality %;
It is 2～35ml/m to the transfer amount of this recording medium that above-mentioned recording medium utilizes the dynamic scan imbibition instrumentation pure water of fixed duration of contact under the 100ms 2, and the pure water under the duration of contact 400ms is 3～40ml/m to the transfer amount of above-mentioned recording medium 2
Print cartridge of the present invention is the recording ink in any ink medium group of above-mentioned the 1st embodiment of the present invention and the 5th embodiment is contained in the container and forms.This print cartridge is fit to be used in the printer that adopts ink-jet recording etc.If utilize the printing ink that is contained in this print cartridge to carry out record, when then on common paper, printing, the image that can obtain high image density, back side concentration is low, colour developing is good, does not have bleeding, in addition, when on the low level and smooth printing of water-retaining capacity, printing, rate of drying improves, and can carry out distinctness and approach the image recording of print.
Moisture retention liquid of the present invention be selected from (1) wrap liquid medium that aqueous liquid medium, (2) they are main component with water, (3) and with water and boiling point be higher than water under 25 ℃ be the liquid parts of liquid as the liquid medium of main component and (4) from comprising the composition identical and being down at least a kind that selects the liquid medium that lacks than this recording ink of the content of solid solids component at 25 ℃ with above-mentioned recording ink.The recording ink of above-mentioned (4) is the type that is used in usually in the ink-vapor recording.
Ink jet recording method of the present invention comprises to recording ink at least in the 1st embodiment and applies stimulation, makes this recording ink flight, and on recording medium the printing ink flight operation of document image;
Above-mentioned recording ink is the recording ink in any ink medium group of above-mentioned the 1st embodiment to the 3 embodiments of the present invention;
Above-mentioned recording medium is the recording medium in any ink medium groups of above-mentioned the 1st embodiment to the 3 embodiments of the present invention.Its result when printing, can obtain high image density, low, the colour developing image that does not have bleeding well of back side concentration on common paper, in addition, when on the low level and smooth printing of water-retaining capacity, printing, also can improve rate of drying, obtain distinctness and approach the image of print.
Ink jet recording method of the present invention when stopping ink-vapor recording for a long time, utilizes above-mentioned moisture retention liquid of the present invention to substitute recording ink in the 2nd embodiment, when restarting ink-vapor recording, utilizes above-mentioned recording ink to substitute above-mentioned moisture retention liquid.The recording ink of above-mentioned (4) is the type that is used in usually in the ink-vapor recording.
In the 3rd embodiment, ink jet recording method of the present invention is supplied with above-mentioned moisture retention liquid of the present invention in the cladding system of the spray nozzle part that covers record-header when stopping ink-vapor recording for a long time.
Even the obstruction of nozzle also can not take place in any ink jet recording method in the 2nd embodiment of the present invention and the 3rd embodiment when stopping using for a long time.
Here, above-mentioned " when stopping using for a long time " is meant utilizing cladding system to cover under the state at (lid) nozzle position, places under the state of stopping using more than 1 day.
Ink jet recording method of the present invention is in the 4th embodiment, at least comprise the recording ink in the ink medium group is applied stimulation, make the flight of this recording ink, and in the printing ink flight operation of document image on the recording medium with will be recorded in the drying process of the image dried on the above-mentioned recording medium;
Above-mentioned ink medium group is any described ink medium group in above-mentioned the 4th embodiment of the present invention and the 5th embodiment.
Ink recorded matter of the present invention is to have the image that utilizes recording ink and form on recording medium;
Above-mentioned recording ink is the recording ink in any ink medium group of above-mentioned the 1st embodiment of the present invention and the 5th embodiment;
Above-mentioned recording medium is the recording medium in any ink medium group of above-mentioned the 1st embodiment of the present invention and the 5th embodiment.
For ink recorded matter of the present invention, when on common paper, printing, can obtain high image density, low, the colour developing image that does not have bleeding well of back side concentration, in addition, when on the low level and smooth printing of water-retaining capacity, printing, can improve rate of drying, and on above-mentioned recording medium, keep distinct and approach the image of print.
Description of drawings
Fig. 1 is the figure that an example of print cartridge of the present invention is shown.
Fig. 2 is the figure that the print cartridge of Fig. 1 also comprises shell (housing).
Fig. 3 is the diagrammatic illustration figure that an example of ink-jet recording device of the present invention is shown.
Fig. 4 is the diagrammatic illustration figure of an example of internal structure that the ink-jet recording device of Fig. 3 is shown.
Fig. 5 is the summary enlarged view that an example of ink gun of the present invention is shown.
Fig. 6 is the sketch chart that the nozzle rows of ink gun of the present invention is shown.
Fig. 7 is the exploded perspective view of the fluid Supplying apparatus in the ink-jet recording device of the present invention.
Fig. 8 is the amplification exploded perspective view of Fig. 7.
Fig. 9 is the side illustration mode chart of pilot trench (subtank).
Figure 10 A is the summary section along the A-A line of Fig. 9.
Figure 10 B is the summary section along the A-A line of Fig. 9.
Figure 11 is the vertical view of keeping the parts top from ink-jet printer of the present invention.
Figure 12 is the diagrammatic illustration figure that shows an example keeping parts of locating ink-jet printer of the present invention.
Figure 13 illustrates the adhesion amount of printing ink group A～C and the graphic representation of the relation of time of drying.
Figure 14 is the water velocity of evaporation time history plot that the printing ink after the printing of printing ink group C is shown.
Figure 15 is the integration evaporated quantity of water time history plot that illustrates among the printing ink group C.
Figure 16 is the figure that be shown the time of drying of printing ink group I among the embodiment, II, III.
Figure 17 illustrates the figure of printing ink group I among the embodiment, evaluation result that II, III print on common paper.
Figure 18 illustrates the figure of printing ink group I among the embodiment, evaluation result that II, III print on common paper.
Figure 19 is the figure that the result of the image color on common paper of Embodiment B-1～B-3 and Embodiment C-1～C-3 and print through is shown.
Figure 20 be illustrate Embodiment B-1～B-3 and Embodiment C-1～C-3 at POD GLOSSCOART 100g/m 2Green on the paper is the adhesion amount at position and the figure of the relation of time of drying on the spot.
Figure 21 is result's the figure that the moisture evaporation speed of embodiment D-1～D-3 and embodiment E-1～E-3 is shown.
Figure 22 is the summary section of an example that the nozzle plate of ink gun of the present invention is shown.
Figure 23 A is the summary section that the nozzle plate of ink gun of the present invention is shown.
Figure 23 B is the summary section that the nozzle plate of ink gun of the present invention is shown.
Figure 23 C is the summary section that the nozzle plate of ink gun of the present invention is shown.
Figure 24 A is the summary section of nozzle plate that the ink gun of comparison is shown.
Figure 24 B is the summary section of nozzle plate that the ink gun of comparison is shown.
Figure 24 C is the summary section of nozzle plate that the ink gun of comparison is shown.
Figure 25 illustrates by the coating of having used divider to apply silicone resin to form the figure of the state of preventing ink film.
Figure 26 A illustrates the coating mouth of needle-like front end of the present invention and to the figure of relation as the coating width of the nozzle plate of coating object.
Figure 26 B illustrates common needle-like front end and to the figure of relation as the coating width of the nozzle plate of coating object.
Figure 27 is the figure that the coating operation of having used divider is shown.
Figure 28 illustrates the figure of formation up to the state of the anti-ink lay of the silicone resin of the desired depth of nozzle inner walls.
Figure 29 is the example that ink gun of the present invention is shown, and the figure that the employing excimer laser is processed to form the state of nozzle bore is shown.
Figure 30 is the figure of the structure of the Excimer Laser Processing Equipment for Chemical Vapor Deposition that uses when being illustrated in the working nozzle hole.
Figure 31 A is the figure that the nozzle in the nozzle plate manufacturing process that illustrates in the manufacture method of ink gun forms the base material of parts.
Figure 31 B is that the surface that is illustrated in resin molding forms SiO 2The figure of the operation of thin film layer.
Figure 31 C is the figure that the operation of coating fluorine class water-resisting agent is shown.
Figure 31 D is the figure that the aerial placement operation behind the waterproof membrane evaporation is shown.
Figure 31 E is the figure that the operation that attaches sealing tape is shown.
Figure 31 F is the figure that the manufacturing procedure of nozzle bore is shown.
Figure 32 is the figure that the summary of the device that uses when making ink gun by the ink gun manufacture method is shown.
Embodiment
(recording ink)
Recording ink of the present invention comprises at least and contains tinting material and resin and being that solid solids component, boiling point are higher and be the liquid component and the water of liquid than water under 25 ℃, also contain other compositions in addition as required under 25 ℃.
＜boiling point is higher than water and is the liquid component of liquid under 25 ℃ 〉
Be higher than water and be the liquid component of liquid under 25 ℃ as above-mentioned boiling point, major part is the high boiling point water-miscible organic solvent that is called as so-called wetting agent, also is equivalent to printing ink control of physical properties agent such as permeate agent, tensio-active agent.
In the present invention, above-mentioned " boiling point is higher than water and is the total content of the liquid component of liquid ", represent the total amount of wetting agent, permeate agent and tensio-active agent particularly under 25 ℃.
Above-mentioned boiling point is higher than water and is 20 quality %s below at the total content of liquid component in above-mentioned recording ink that is liquid under 25 ℃, is preferably below the 15 quality %, according to circumstances can also be 0 quality % (not adding).Above-mentioned boiling point is higher than water and is that the content of liquid component of liquid is few more under 25 ℃, and the time of drying of printing ink is just short more, and still, the obstruction for the drying that prevents because of nozzle causes needs stricter control.In addition, even the paper that the few difficulties such as printing ink hectograph White Board of the addition of above-mentioned wetting agent and above-mentioned permeate agent absorb water also can promptly carry out drying, thus the image that acquisition has the glossy excellence.But, do not add fully under the situation of high capillary printing ink of tensio-active agent, permeate too slow, dry slack-off.
If above-mentioned content is higher than 20 quality %, then the rate of drying of coated paper for printing such as hectograph White Board reduces, and the print through of common paper increases sometimes.But final boiling point in the liquid component is higher than water and is that the amount of liquid component of liquid is few relatively more under 25 ℃ still comparatively speaking, and drying property just improves.
Wherein, be higher than water and be the liquid component of liquid under 25 ℃, do not have particular restriction with regard to all comprising so long as boiling point is higher than the water-miscible organic solvent of water as above-mentioned boiling point.In addition, permeate agent, tensio-active agent etc. are so long as boiling point is higher than water and be that liquid is just includable under 25 ℃.Generally speaking, purpose is the amount that more is difficult to exsiccant liquid than water by reducing as far as possible, even the such few paper of water-retaining capacity of printing also can shorten time of drying.It is generally acknowledged that the drying property to the printing of the paper of ink-vapor recording is that infiltration is dry, the contribution of printing ink evaporation seldom, but current result hint also has the contribution of evaporation under the drying of short period, still, its details and indeterminate, it is as described below to infer mechanism.In addition, under the situation of the offset paper that such water-retaining capacity is low, the high capillary printing ink that perviousness is low is compared with the printing ink of low surface tension, and is dry slack-off.Can think that in the present invention moistening dosage is the many situations of printing ink adhesion amount of unit surface to the contribution of time of drying significantly.
-wetting agent (high boiling point water-miscible organic solvent)-
Be higher than water and be the representational so-called wetting agent of the liquid component of liquid under 25 ℃ as above-mentioned boiling point, as long as under 25 ℃, be liquid, just there is not particular restriction, can suitably select according to purpose, for example, can enumerate polyalcohols, polyol alkyl ether class, polyvalent alcohol aryl ethers, nitrogen-containing heterocycle compound, amides, amine, sulfocompound class, propylene carbonate, NSC 11801 etc.These materials can use a kind separately, also can use simultaneously more than 2 kinds.
As above-mentioned polyalcohols, for example, can enumerate ethylene glycol, glycol ether, triglycol, polyoxyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1, ammediol, 1,3 butylene glycol, 2,3-butyleneglycol, 1,4-butyleneglycol, 3-methyl isophthalic acid, 3-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, 2-methyl-2,4-pentanediol, Tetraglycol 99, glycerine, 1,2,6-hexanetriol, 1,2,4-trihydroxybutane, 1,2,3-trihydroxybutane, tetramethylolmethane (petriol) etc.
As above-mentioned polyol alkyl ether class, for example, can enumerate ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Tetraglycol 99 monomethyl ether, dihydroxypropane single-ether etc.
As above-mentioned polyvalent alcohol aryl ethers, for example, can enumerate ethyleneglycol monophenylether, ethylene glycol monobenzyl ether etc.
As above-mentioned nitrogen-containing heterocycle compound, for example, can enumerate N-N-methyl-2-2-pyrrolidone N-, N-hydroxyethyl-2-Pyrrolidone, 2-Pyrrolidone, 1,3-methylimidazole alkane ketone, ε-Ji Neixianan etc.
As above-mentioned amides, for example, can enumerate methane amide, N-methylformamide, N, dinethylformamide etc.
As above-mentioned amine, for example, can enumerate monoethanolamine, diethanolamine, trolamine, mono aminoethane, diethylamine, triethylamine etc.
As above-mentioned sulfocompound class, for example, can enumerate methyl-sulphoxide, tetramethylene sulfone, sulphur di-alcohol, thiodiglycol etc.
Wherein, from the consideration of ink jet stability, preferably glycerine, 2-Pyrrolidone, glycol ether, sulphur di-alcohol, polyoxyethylene glycol, triglycol, 1,2,6-hexanetriol, 1,2,4-trihydroxybutane, tetramethylolmethane (petriol), 1,5-pentanediol, N-N-methyl-2-2-pyrrolidone N-, 1,3 butylene glycol, 3-methyl isophthalic acid, the 3-butyleneglycol, wherein, special preferably glycerine, 1,3 butylene glycol, 3-methyl isophthalic acid, 3-butyleneglycol, 2-Pyrrolidone.
Be higher than water as the boiling point of main component and be below the 20 quality % under 25 ℃ by making, be preferably below the 15 quality %, can improve drying property at the total content that is the liquid component of liquid with above-mentioned wetting agent.As what add as required is the water of liquid, the composition beyond the wetting agent under 25 ℃, and permeate agent, the tensio-active agent of the following stated arranged.Here, be that liquid is meant that normal temperature, normal pressure (25 ℃, 1 normal atmosphere) in the environment for use of common ink-vapor recording are the meaning of liquid down under 25 ℃.But, because the addition of composition beyond the wetting agent is few, even therefore boiling point is higher than water and is that the total amount of liquid component of liquid is similar to moistening dosage under 25 ℃, also almost not variation.
In addition, when supplementary units such as heating, air-supply arrangement were set when the drying to printing ink, the content of wetting agent can reach about 30 quality %.
On the other hand, if wetting agent is less than 10 quality %, when carrying (carriage) operation for a long time, when printing the nozzle that has only this color in other colors and not printing, because the nozzle position drying of the color of not printing can cause spray nozzle clogging.At this moment, the place beyond the recording medium must be carried out sky continually and sprayed, and carries out 1 time empty the injection during preferably every at least printing A4 size, carries out 1 sky injection during more preferably every printing 1 row.It also is to prevent one of nozzle position exsiccant method that water is provided in the lid at covering nozzles position when stopping using for a long time in addition.
For the few printing ink of such a wetting agent, make it mechanically be full of holdout device, thereby the practice of keeping the reliability of injection is preferred.
But, the polymer emulsion that forms in polymer particles, the containing the colorant of water-insoluble or slightly water-soluble of the present invention's use as tinting material, even injection is also more stable under low moistening agent concentration, not necessarily need above-mentioned such special holdout device.
-permeate agent-
As above-mentioned permeate agent,, all comprise and calculate being higher than water and being in the liquid component of liquid under 25 ℃ at above-mentioned boiling point of the present invention so long as boiling point is higher than water and be liquid under 25 ℃.In addition, as mentioned above,, on calculating, also can omit at the addition of permeate agent after a little while.
As above-mentioned permeate agent, can use the polyol compound or the glycol ethers compound of carbonatoms 8～11.At least a of these polyol compounds and glycol ethers compound is to have to improve the speed and the effect that prevents bubble of permeating in paper, has the portion water soluble compound of the solubleness of 0.1～4.5 quality % in 25 ℃ water.
As the polyol compound of above-mentioned carbonatoms 8～11, for example, can enumerate 2-ethyl-1,3-hexylene glycol, 2,2,4-trimethylammonium-1,3-pentanediol etc.
As above-mentioned glycol ethers compound, for example, can enumerate polyol alkyl ether compound, polyvalent alcohol aryl ethers compound etc.
As above-mentioned polyol alkyl ether compound, for example, can enumerate ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, Tetraglycol 99 monomethyl ether, dihydroxypropane single-ether etc.
As above-mentioned polyvalent alcohol aryl ethers compound, for example, can enumerate ethyleneglycol monophenylether, ethylene glycol monobenzyl ether etc.
Be higher than water and be preferably 0～10 quality % as above-mentioned boiling point, more preferably 0.5～5 quality % at the content of permeate agent in above-mentioned recording ink that under 25 ℃ is the liquid component of liquid.But boiling point is higher than water and is 20 quality %s below at the total content that is the liquid component of liquid under 25 ℃, is preferably below the 15 quality %.
-tensio-active agent-
As mentioned above, above-mentioned tensio-active agent adds as required, if boiling point is higher than water and be liquid under 25 ℃, then comprises and calculate at above-mentioned boiling point of the present invention being higher than water and being in the liquid component of liquid under 25 ℃.As mentioned above, if the addition of tensio-active agent is few, on calculating, also can omit.
As above-mentioned tensio-active agent, there is not particular restriction, can be according to the kind of tinting material or the combination of wetting agent, permeate agent etc., never damage according to purpose in the tensio-active agent of dispersion stabilization and suitably select, but when printing on printing, special preferred surface tension force is low, the tensio-active agent that levelling property is high, at least a kind that is selected from silicone based tensio-active agent and the fluorine class tensio-active agent is suitable.Wherein preferred especially fluorine class tensio-active agent.
In addition, when on non-porous base materials such as polyester chips, printing,, then can improve wetting property, levelling property, drying property, image homogeneity are brought desirable influence recording medium if add the surface tension that tensio-active agent reduces printing ink in advance.
As above-mentioned fluorine class tensio-active agent, the carbonatoms that fluorine replaces is preferably 2～16, and more preferably 4～16.If above-mentioned fluorine alternate c atoms number is lower than 2, can not obtain the effect of fluorine sometimes, if greater than 16, then produce the problem of aspects such as printing ink keeping quality sometimes.
As above-mentioned fluorine class tensio-active agent, for example, can enumerate perfluoro alkyl sulfonic acid compound, perfluoroalkyl carbon compound, perfluoralkyl phosphate compound, perfluoroalkyl ethylene oxide adduct and side chain and have polyoxyalkylene ether polymer compound of perfluoroalkyl ether etc.Wherein, the polyoxyalkylene ether polymer compound whipability that side chain has the perfluoroalkyl ether is low, thereby preferred especially.
As above-mentioned perfluoro alkyl sulfonic acid compound, for example, can enumerate perfluoro alkyl sulfonic acid, fluorinated alkyl sulfonate etc.
As above-mentioned perfluoroalkyl carbon compound, for example, can enumerate perfluoro carboxylic acid, perfluoroalkyl carboxylate etc.
As above-mentioned perfluoralkyl phosphate compound, for example, can enumerate the salt of perfluoralkyl phosphate, perfluoralkyl phosphate etc.
Have the polyoxyalkylene ether polymer compound of perfluoroalkyl ether as above-mentioned side chain, can enumerate the salt etc. that sulfuric acid, side chain that polyoxyalkylene ether polymer, side chain that side chain has the perfluoroalkyl ether have the polyoxyalkylene ether polymer of perfluoroalkyl ether have the polyoxyalkylene ether polymer of perfluoroalkyl ether.
As the counter ion of the salt of these fluorine class tensio-active agents, can enumerate Li, Na, K, NH 4, NH 3CH 2CH 2OH, NH 2(CH 2CH 2OH) 2, NH (CH 2CH 2OH) 3Deng.
As above-mentioned fluorine class tensio-active agent, can also suitably use the synthetic material, also can use commercially available product.
As this commercially available product, for example, can enumerate サ one Off ロ Application S-111, S-112, S-113, S-121, S-131, S-132, S-141, S-145 (being Asahi Glass Co., Ltd makes); Off Le ラ one De FC-93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431 (being Sumitomo ス リ one エ system Co., Ltd. makes); メ ガ Off ア Star Network F-470, F-1405, F-474 (being Dainippon Ink. ﹠ Chemicals Inc makes) Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, UR (being DuPont company makes); FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW (being the ネ オ ス of Co., Ltd. makes); PF-151N (manufacturing of オ system ノ バ company) etc., wherein, from good printing quality, especially significantly improve color developing, the viewpoint of the equalization of paper is considered the PF-151N that FT-110, FT-250, FT-251, FT-400S, FT-150, FT-400SW and the オ system ノ バ company that the preferred especially ネ オ ス of Co., Ltd. makes makes.
As the object lesson of above-mentioned fluorine class tensio-active agent, the material of representing with following structural formula is suitable.
(1) anionic property fluorine class tensio-active agent
Figure A20071013790300201
Wherein, in said structure, Rf represents the mixture of the fluorine-containing hydrophobic group represented with following structural formula.A represents-SO 3X ,-COOX or-PO 3(wherein, X is a counter anion to X, can enumerate hydrogen atom, Li, Na, K, NH particularly 4, NH 3CH 2CH 2OH, NH 2(CH 2CH 2OH) 2, or NH (CH 2CH 2OH) 3).
Figure A20071013790300211
And
Figure A20071013790300212
(Rf’-O nPOO·X) m
Wherein, in the said structure formula, the fluoro-containing group that Rf ' expression is represented with following structural formula.X represents the meaning same as described above.N represents 1 or 2 integer, and m represents 2-n.
FCF 2CF 2nCH 2CH 2-
Wherein, in the said structure formula, n represents 3～10 integer.
Rf’-S-CH 2CH 2-COO·X
Wherein, in the said structure formula, Rf ' and X represent the meaning same as described above.
Rf’-SO 3·X
Wherein, in the said structure formula, Rf ' and X represent the meaning same as described above.
(2) nonionic fluorine class tensio-active agent
Rf-OCH 2CH 2O nH
Wherein, in the said structure formula, Rf represents the meaning same as described above.N represents 5～20 integer.
Rf’-OCH 2CH 2O nH
Wherein, in the said structure formula, the meaning that Rf ' expression is same as described above.N represents 1～40 integer.
(3) both sexes fluorine class tensio-active agent
Figure A20071013790300213
Wherein, in the said structure formula, Rf represents the meaning same as described above.
(4) oligomeric fluorine class tensio-active agent
Figure A20071013790300221
Wherein, in the said structure formula, Rf " fluoro-containing group represented with following structural formula of expression.N represents 0～10 integer.X represents the meaning same as described above.
FCF 2CF 2nCH 2-
Wherein, in the said structure formula, n represents 1～4 integer.
Figure A20071013790300222
Wherein, in the said structure formula, Rf " the expression meaning same as described above.L represents 0～10 integer, and m represents 0～10 integer, and n represents 0～10 integer.
As above-mentioned silicone based tensio-active agent, there is not particular restriction, can suitably select according to purpose, preferred also Undec material under high pH, for example, can enumerate modified side chain polydimethylsiloxane, two terminal-modified polydimethyl silane, single terminal-modified polydimethylsiloxane, side chain two terminal-modified polydimethylsiloxanes etc., as the modification group, material with polyoxyethylene thiazolinyl, polyoxyethylene polyoxytrimethylene base as the water system tensio-active agent owing to show good properties, thereby preferred especially.
As such tensio-active agent, can also suitably use the synthetic material, also can use commercially available product.
As this commercially available product, for example, can easily obtain from PVC Star Network ケ ミ one Co., Ltd., シ リ コ one Application Co., Ltd. of SHIN-ETSU HANTOTAI, eastern Le ダ ウ コ one ニ Application グ シ リ コ one Application Co., Ltd. etc.
As above-mentioned organic silicon modified by polyether class tensio-active agent, be not particularly limited, can suitably select according to purpose, for example, can be set forth in the compound of introducing the polyalkylene oxide hydrocarbon structure that following structural formula represents on the Si side chain of dimethyl polysiloxane etc.
Figure A20071013790300223
X＝-R(C 2H 4O)a(C 3H 6O)bR’
Wherein, in said structure, m, n, a and b represent integer.R and R ' expression alkyl, alkylidene group.
As above-mentioned organic silicon modified by polyether compound, can use commercially available product, for example, can enumerate KF-618, KF-642, KF643 (being Shin-Etsu Chemial Co., Ltd makes) etc.
In addition, except above-mentioned fluorine class tensio-active agent and silicone based tensio-active agent, can also use anionic surfactant, nonionic surfactant, amphoterics etc.
As above-mentioned anionic surfactant, for example, can enumerate the salt of polyethylene oxide alkyl ethers acetate, dodecylbenzene sulfonate, sulphosuccinates, lauroleate, polyethylene oxide alkyl ethers sulfuric ester etc.
As above-mentioned nonionic class tensio-active agent, for example, can enumerate alkyne diol (acetylene glycol) class tensio-active agent, polyethylene oxide alkyl ethers, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan-fatty acid ester etc.
As above-mentioned acetylenic diols tensio-active agent, for example, can enumerate 2,4,7,9-tetramethyl--5-decene-4,7-glycol, 3,6-dimethyl-4-octene-3,6-glycol, 3,5-dimethyl-1-hexene-3-ol etc.As the commercially available product of this acetylenic diols tensio-active agent, for example can enumerate サ one Off イ ノ one Le 104,82,465,485, TG of エ ア one プ ロ ダ Network Star company (U.S.) etc.
As above-mentioned amphoterics, for example, can enumerate lauryl aminopropionate, lauryl dimethyl trimethyl-glycine, stearyl dimethyl betaine, lauryl dihydroxy ethyl trimethyl-glycine, lauryl dimethyl amine oxide, myristyl dimethyl amine oxide, stearyl dimethyl amine oxide, dihydroxy ethyl lauryl amine oxide, polyoxyethylene Oleum Cocois alkyl dimethyl amine oxide, dimethyl alkyl (coconut) trimethyl-glycine, dimethyl lauryl betaine etc.
As such tensio-active agent, as commercially available product, can easily obtain from daylight ケ ミ カ Le ズ Co., Ltd., Japanese エ マ Le ジ ヨ Application Co., Ltd., Nippon Shokubai Co., Ltd, Dong Bang KCC, Kao Corp, ア デ カ Co., Ltd., ラ イ オ Application Co., Ltd., blue or green wood oil fat Co., Ltd., Sanyo Chemical Industries, Ltd. etc.
Above-mentioned tensio-active agent is not limited to these materials, can use separately, can also mix multiple use.When being not easy to be dissolved in the recording ink separately, also can make it solvable and existence stably by mixing.
In these tensio-active agents, the material of representing with following structural formula (1)～(5) is suitable.
R 1-O-(CH 2CH 2O) h-R 2... structural formula (1)
Wherein, in said structure formula (1), R 1Expression carbonatoms 6～14 can branching alkyl or carbonatoms 6～14 can branching perfluoroalkyl.R 2The alkyl of expression hydrogen atom or carbonatoms 1～4 that can branching.H represents 5～20 integer.
R 1-COO-(CH 2CH 2O) h-R 2... structural formula (2)
Wherein, in said structure formula (2), R 1Expression carbonatoms 6～14 can branching alkyl.R 2The alkyl of expression hydrogen atom or carbonatoms 1～4 that can branching.H represents 5～20 integer.
Figure A20071013790300241
... structural formula (3)
Wherein, in said structure formula (3), R 3The expression alkyl for example, can be enumerated the alkyl of carbonatoms 6～14 that can branching etc.K represents 5～20 integer.
Figure A20071013790300242
... structural formula (4)
Wherein, in said structure formula (4), R 4The expression alkyl, for example, the alkyl of the carbonatoms 6～14 that expression can branching.L represents 5～10 integer, and p represents 5～20 integer.Propylene glycol chain and glycol chain can also carry out block polymerization or random polymerization.
Figure A20071013790300243
... structural formula (5)
Wherein, in said structure formula (5), q and r represent 5～20 integer.
The content of above-mentioned tensio-active agent in above-mentioned recording ink is preferably 0.01～3.0 quality %, more preferably 0.5～2 quality %.But boiling point is higher than water and is 20 quality %s below at the total content that is the liquid component of liquid under 25 ℃, is preferably below the 15 quality %.
If above-mentioned content is lower than 0.01 quality %, then do not add the effect of tensio-active agent sometimes, if be higher than 3.0 quality %, then be higher than the necessary amount of infiltration on the recording medium, the reduction or the print through that produce image color sometimes.
＜contain tinting material and resin and be the solid solids component under 25 ℃
The total content of the resinous principle in the above-mentioned solids component contains tinting material and resin and being that the solid solids component is more than the 40 quality % under 25 ℃, is preferably more than the 70 quality %, more preferably more than the 80 quality % with respect to above-mentioned.In addition, be preferably below the 95 quality %.If above-mentioned content is lower than 40 quality %, the stability of tinting material and reflecting feel are poor sometimes.On the other hand, in order to improve image color to a certain extent, the content of above-mentioned tinting material must be for more than the 5 quality % with respect to the total amount of above-mentioned solids component.
The content that improves the resinous principle in the solids component like this is in order to improve fixation performance, image distinctiveness, glossiness.
Here, above-mentioned resinous principle is meant the polymeric solid composition beyond the colourant molecule with chromophoric group, comprises tinting material, also comprises making tinting material dispersive resin.In addition, also comprise the resin emulsion that adds as required certainly.Promptly, in " total content of the resinous principle in the above-mentioned solids component is with respect to the total amount of above-mentioned solids component ", " when calculating the total content of resinous principle ", comprise the colourant molecule with chromophoric group (for example pigment molecule) in the tinting material, and tinting material dispersive resin is also contained in the amount of resinous principle.
In addition, be that solid is meant that normal temperature, normal pressure (25 ℃, 1 normal atmosphere) in the environment for use of common ink jet printing are solid down under 25 ℃.
In the present invention, the total amount of above-mentioned " contain tinting material and resin and be the total content of solid solids component under 25 ℃ " expression tinting material and resin.
-resin-
As above-mentioned resin, as long as be solid down, just there is not particular restriction at 25 ℃, can suitably select according to purpose, but from improving the viewpoint consideration of resin content, preferred resin particulate.
For above-mentioned resin particle, when making printing ink, use to be dispersed in the particulate that exists as the resin emulsion in the water of external phase.As required, can also in resin emulsion, contain the such dispersion agent of tensio-active agent.
Content (content of the resin particle in the resin emulsion solution is not the content in the recording ink after making) as the resin particle of above-mentioned disperse phase composition generally is preferably 10～70 quality %.
In addition, consider especially to be used for ink-jet recording device that the particle diameter preferred volume median size of above-mentioned resin particle is 10～1,000nm, more preferably 100～300nm, more preferably 50～200nm.These are the particle diameters in the resin emulsion, still, under the situation of stable recording ink, the not too big difference of particle diameter in the resin emulsion and the resin particle particle diameter in the recording ink.Above-mentioned volume average particle size is big more, can increase the addition of emulsion more.If above-mentioned volume average particle size is lower than 100nm, then can not improve the addition of emulsion sometimes, if greater than 300nm, reliability descends sometimes.But the emulsion of particle diameter neither can be used scarcely beyond this scope.These are the general tendencies that do not depend on the emulsion kind.
Especially as the high resin particulate loading, obtain high image quality in order to utilize non-porous medium, the resin particle particle diameter is preferably 50～200nm.
Here, above-mentioned volume average particle size for example can utilize sreen analysis device (マ イ Network ロ ト ラ Star Network MODEL UPA9340, Nikkiso Company Limited makes) to measure.
Specifically, the emulsion aqueous solution is diluted in the signal level optimum range, at transparency-YES, measure under the condition such as Reflactive Index 1.49, Partial Densityl.19, SphericalParticles-YES, medium-water.Wherein, with 50% value as volume average particle size.
Above-mentioned water-dispersed resin does not preferably make above-mentioned water-dispersion tinting material flow (preventing the inequality (foaming) of image color) on non-porous substrate surfaces such as polyester film, and have in the effect of recording medium surface photographic fixing or the effect of auxiliary photographic fixing, form at normal temperatures and film, the fixation performance of tinting material is improved.Therefore, the minimum film-forming temperature of above-mentioned water-dispersed resin (MFT) is preferably below the normal temperature, more preferably below 20 ℃.
Resin particle (water-dispersed resin) as above-mentioned disperse phase does not have particular restriction, can suitably select as required, for example, can enumerate condensation class synthetic resins, addition class synthetic resins, natural high moleculer eompound etc.As above-mentioned condensation class synthetic resins, for example, can enumerate vibrin, urethane resin, poly epoxy resin, polyamide resin, polyether resin, silicone resin etc.As above-mentioned addition class synthetic resins, for example, can enumerate polyolefin resin, polystyrene resins, polyvinyl alcohol resin, polyvinyl esters resin, polyacrylic acid resinoid, unsaturated carboxylic acid resinoid etc.As above-mentioned natural high moleculer eompound, for example, can enumerate cellulose family, rosin based, natural rubber etc.
Above-mentioned water-dispersed resin can use homopolymer, also can use multipolymer, can also use the complex class resin, can use any in phase structure type and hud typed, the power feed type emulsion.
As above-mentioned water-dispersed resin, can use resin itself to have hydrophilic radical, have from dispersed material, resin itself and do not have dispersiveness, provide dispersed material by tensio-active agent or resin with hydrophilic group.Wherein, the emulsion of the resin particle that obtains of the emulsification of ionomer by vibrin or urethane resin or unsaturated monomer and suspension polymerization is best.In addition, acrylic resin, vinylformic acid silicone resin emulsion are best.Under the situation of unsaturated monomer emulsion polymerization, make resin emulsion owing to utilizing the water that has added unsaturated monomer, polymerization starter, tensio-active agent, chain-transfer agent, sequestrant, pH regulator agent etc. to react, therefore can easily make water-dispersed resin, owing to replace resin structure easily, therefore reach destination properties easily.
As above-mentioned unsaturated monomer, for example, can separately and make up multiple use unsaturated carboxylic acid class, (methyl) acrylate monomer class, (methyl) acrylamide monomer class, aromatic vinyl monomer class, ethene cyanogen compound monomer class, vinyl monomer class, allylic cpd monomer class, olefinic monomer class, diene monomers class, have the oligopolymer class of unsaturated carbon etc.By making up these monomers, mildly improved properties is carried out polyreaction, graft reaction by utilizing the oligomeric polymerization starter, the characteristic of all right modified resin.
As above-mentioned unsaturated carboxylic acid class, for example, can enumerate vinylformic acid, methacrylic acid, methylene-succinic acid, fumaric acid, toxilic acid etc.
As above-mentioned simple function (methyl) esters of acrylic acid, for example, can enumerate methyl methacrylate, Jia Jibingxisuanyizhi, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, the methacrylic acid n-pentyl ester, the methacrylic isoamyl valerate, the just own ester of methacrylic acid, methacrylic acid 2-ethylhexyl, Octyl methacrylate, decyl-octyl methacrylate, lauryl methacrylate, the methacrylic acid stearyl, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, glycidyl methacrylate, methacrylic acid 2-hydroxyl ethyl ester, methacrylic acid 2-hydroxypropyl acrylate, dimethylaminoethyl methacrylate, the methacryloxyethyl leptodactyline, the 3-methacryloxypropyl trimethoxy silane, methyl acrylate, ethyl propenoate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, the vinylformic acid n-pentyl ester, the vinylformic acid isopentyl ester, the just own ester of vinylformic acid, 2-EHA, Octyl acrylate, decyl acrylate, dodecylacrylate, the vinylformic acid stearyl, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, glycidyl acrylate, vinylformic acid 2-hydroxyl ethyl ester, vinylformic acid 2-hydroxypropyl acrylate, the vinylformic acid dimethylamino ethyl ester, acryloxy ethyl-trimethyl ammonium salt etc.
As above-mentioned polyfunctional (methyl) esters of acrylic acid, for example, can enumerate Ethylene glycol dimethacrylate, diethyleneglycol dimethacrylate(DEGDMA), the dimethacrylate triglycol ester, the dimethacrylate macrogol ester, dimethacrylate 1, the 3-butanediol ester, dimethacrylate 1, the 4-butanediol ester, dimethacrylate 1,6-hexylene glycol ester, the dimethacrylate DOPCP, dipropyleneglycol dimethacrylate, dimethacrylate polypropylene glycol ester, dimethacrylate polytetramethylene glycol ester, 2,2 '-two (4-methacryloxy diethoxy phenyl) propane, trimethylolpropane trimethacrylate, the trimethylolethane trimethacrylate methacrylic ester, the diacrylate macrogol ester, the diacrylate triglycol ester, diacrylate 1, the 3-butanediol ester, diacrylate 1, the 4-butanediol ester, diacrylate 1,6-hexylene glycol ester, diacrylic acid pentyl diol ester, diacrylate 1,9-nonanediol ester, diacrylate polypropylene glycol ester, 2,2 '-two (4-acryloxy propoxy-phenyl) propane, 2,2 '-two (4-acryloxy diethoxy phenyl) propane Viscoat 295, the trimethylolethane trimethacrylate acrylate, the tetramethylol methane triacrylate, two (trishydroxymethyl) tetraacrylate, the tetramethylol methane tetraacrylate, pentaerythritol tetracrylate, six vinylformic acid dipentaerythritol ester etc.
As above-mentioned (methyl) acrylamide monomer class, for example, can enumerate acrylamide, Methacrylamide, N,N-DMAA, methylene-bisacrylamide, 2-acrylamide-2-methyl propane sulfonic acid etc.
As above-mentioned aromatic vinyl monomer class, for example, can enumerate vinylbenzene, alpha-methyl styrene, Vinyl toluene, 4-t-butyl styrene, chloro-styrene, vinyl phenylmethylether, vinyl naphthalene, Vinylstyrene etc.
As above-mentioned vinyl cyanide compound monomer class, for example, can enumerate vinyl cyanide, methacrylonitrile etc.
As above-mentioned allylic cpd monomer class, for example, can enumerate allyl sulphonic acid and salt thereof, allyl amine, chlorallylene, diallyl amine, diallyl dimethyl ammonium salt etc.
As above-mentioned olefinic monomer class, for example, can enumerate ethene, propylene etc.
As above-mentioned diene monomers class, for example, can enumerate divinyl, chloroprene etc.
As the vinyl monomer class, for example, can enumerate vinyl acetate between to for plastic, vinylidene chloride, vinylchlorid, vinyl ether, vinyl ketone, vinyl pyrrolidone, vinyl sulfonic acid or its salt, vinyltrimethoxy silane, vinyltriethoxysilane etc.
As above-mentioned oligopolymer class with unsaturated carbon; for example, polyester oligomer that can enumerate the styrene oligomer with methacryloyl, styrene-acrylonitrile oligopolymer, methyl methacrylate oligopolymer, dimethyl siloxane oligopolymer, has acryl etc. with methacryloyl with methacryloyl with methacryloyl.
Above-mentioned water-dispersed resin can cause that under strong basicity, strong acidic condition dispersion destroys or hydrolysis equimolecular chain break, therefore, pH is preferably 4～12, especially from considering with the Combination aspect of water-dispersion tinting material, pH more preferably 6～11, and further preferred 7～9.
As above-mentioned resin emulsion, can also use commercially available product.As this commercially available resin emulsion, for example, can enumerate マ イ Network ロ ジ エ Le E-1002, E-5002 (styrene-propene acid resin emulsion, Japan ペ イ Application ト Co., Ltd. makes), ボ Application コ one ト 4001 (acrylic resin emulsions, Dainippon Ink. ﹠ Chemicals Inc makes), ボ Application コ one ト 5454 (styrene-propene acid resin emulsion, Dainippon Ink. ﹠ Chemicals Inc makes), SAE-1014 (styrene-propene acid resin emulsion, Japan ゼ オ Application Co., Ltd. makes), サ イ PVC ノ one Le SK-200 (acrylic resin emulsion, サ イ デ Application KCC makes), プ ラ イ マ Le AC-22, AC-61 (acrylic resin emulsion, ロ one system ア Application De Ha one ス makes), Na イ Network リ Le SBCX-2821,3689 (the silicone based resin emulsions of vinylformic acid, Japan イ Application キ makes Co., Ltd. and makes), #3070 (methyl methacrylate polymer resin emulsion, Mikoku Pigment Co., Ltd. makes) etc.Wherein, from the good viewpoint of fixation performance, preferred especially vinylformic acid organic silicon emulsion.
The second-order transition temperature of the resinous principle in the aforesaid propylene acid organic silicon emulsion is preferably below 25 ℃, more preferably below 0 ℃.If above-mentioned second-order transition temperature is higher than 25 ℃, can cause that resin itself becomes fragile, and becomes the cause of fixation performance variation.The reduction of fixation performance especially appears on the printing of level and smooth and difficult suction sometimes.But,, also not necessarily cannot use even second-order transition temperature is higher than 25 ℃.
Above-mentioned second-order transition temperature for example can utilize differential scanning calorimeter (Electric Co., Ltd of science makes) to measure.
Particularly, begin to heat up from about-50 ℃, under the temperature that creates a difference, try to achieve by the resin sheet of the electric differential scanning calorimeter of Neo-Confucianism with the Air drying film of the resin emulsion aqueous solution.
-tinting material-
As above-mentioned tinting material, as long as under 25 ℃, be solid, just there is not particular restriction, can also suitably use pigment and dyestuff.
If use pigment as above-mentioned tinting material, can make the printing ink of photostabilization excellence.As above-mentioned pigment, there is not particular restriction, the pigment that can use common ink-jet to use, but the material of preferably enumerating below.
(1) given the pigment of hydrophilic radical in surface of pigments
(2) make polymer particles contain the colorant of water-insoluble or slightly water-soluble and the pigment of the polymer emulsion type made
(3) utilization has the microcapsule-type pigment of the resin-coated pigment of hydrophilic radical
For the pigment of above-mentioned (1), be to the surface of pigment carry out surface modification and make directly or by other atomic groups in conjunction with at least a kind of hydrophilic radical.This surface modification can utilize the surface chemistry ground that makes pigment in conjunction with specific functional group (functional groups such as sulfonic group or carboxyl) or utilize hypohalous acid or its salt at least a kind to carry out the method for wet oxidation processing etc.Wherein, especially preferably make carboxyl be incorporated into surface of pigments, be scattered in the mode in the water.Like this, pigment is combined carboxyl by surface modification, and therefore, not only dispersion stabilization is improved, and can obtain high-quality printing quality, and the water tolerance of the recording medium after the printing has obtained further raising simultaneously.
Therefore in addition, the redispersibility excellence in this mode behind the ink setting stops printing for a long time, also can not cause obstruction during near the moisture evaporation of the printing ink the nozzle of ink gun, utilizes simple cleaning operation just can easily carry out good printing.
The volume average particle size of above-mentioned self-dispersion type pigment is preferably 0.01～0.16 μ m in printing ink.
For example,, preferably have ionic carbon black as the self-dispersion type carbon black, charged for the carbon black of anionic property or charged for the carbon black of cationic be suitable.
As above-mentioned anionic property hydrophilic radical, for example, can enumerate-COOM ,-SO 3M ,-PO 3HM ,-PO 3M 2,-SO 2NH 2,-SO 2(wherein, M represents hydrogen atom, basic metal, ammonium or organic ammonium to NHCOR.R represent carbonatoms 1～12 alkyl, can have substituent phenyl and maybe can have substituent naphthyl) etc.Wherein, preferred use-COOM ,-SO 3M is combined in the material on coloured pigment surface.
In addition, " M " in the above-mentioned hydrophilic radical as basic metal, for example, can enumerate lithium, sodium, potassium etc.As above-mentioned organic ammonium, for example, can enumerate one to trimethyl ammonium, to triethyl ammonium, one to three methanol ammonium hydroxide.As the method that makes above-mentioned charged coloured pigment for anionic property, to the method for coloured pigment surface importing-COONa for example can enumerate utilize clorox to coloured pigment carry out oxide treatment method, utilize the sulfonated method, make the method for diazonium  reactant salt.
As above-mentioned cationic hydrophilic radical, for example, preferred quaternary ammonium group, the more preferably following quaternary ammonium group of enumerating, in the present invention, wherein any combines with carbon blacksurface and the material that forms all is suitable as colorant.
-NH 3 +、-NR 3 +、
As making the above-mentioned cationic self-dispersion type sooty method that combines hydrophilic radical, there is not particular restriction, can suitably select according to purpose, for example, as the N-ethyl pyridinyl bonded method that following structural formula is represented, can enumerate the method for utilizing 3-amino-N-ethylpyridine bromide  treated carbon black.
Above-mentioned hydrophilic radical can also pass through other atomic groups and sooty surface bonding.As other atomic groups, for example, can enumerate carbonatoms 1～12 alkyl, can have substituent phenyl and maybe can have substituent naphthyl., for example, can enumerate-C by other atoms and carbon blacksurface bonded object lesson as above-mentioned hydrophilic radical 2H 4COOM (wherein, M represents basic metal or quaternary ammonium) ,-PhSO 3(wherein, Ph represents phenyl to M.M represents basic metal or quaternary ammonium) ,-C 5H 10NH 3 +Deng.
In the pigment of above-mentioned (2), the polymer emulsion that contains colorant be illustrated in the emulsion of the surface adsorption pigment of enclosing the emulsion of pigment in the polymer particles and making polymer particles at least any.For example, can enumerate the emulsion etc. that the spy opens 2001-139849 communique record.
At this moment, need not to make whole pigment to enclose and/or be adsorbed in the polymer particles, in the scope of not damaging effect of the present invention, this pigment can also be scattered in the emulsion.
Above-mentioned " water-insoluble or slightly water-soluble " is meant that under 20 ℃ with respect to the water of 100 mass parts, colorant does not dissolve more than the 10 quality %.In addition, above-mentioned what is called " dissolving " be meant by range estimation can not be on aqueous solution top layer or lower floor find the separation or the settled meaning of colorant.
As the polymkeric substance that forms above-mentioned polymer emulsion, there is not particular restriction, can suitably select according to purpose, for example, can enumerate that vinylic polymers, polyester polymer, polyurethane polymer, spy are opened the 2000-53897 communique, the spy opens the disclosed polymkeric substance of 2001-139849 communique etc.Wherein, special preferred vinyl base polymer, polyester polymer.
The volume average particle size that contains the polymer particles (toner) of above-mentioned colorant is preferably 0.01～0.16 μ m in above-mentioned printing ink.
If use the pigment of above-mentioned (2), then can obtain the printing ink of photostabilization, fixation performance excellence.
The pigment of above-mentioned (3) is to utilize hydrophilic water-insoluble resin-coated pigment, and the resin layer by this surface of pigments carries out hydrophilicity-imparting treatment makes the pigment of colo(u)rant dispersion in water, for example, can enumerate the pigment etc. that the spy opens the record of 2002-67473 communique.
If use the pigment of above-mentioned (3), then can obtain the printing ink of photostabilization, fixation performance excellence.
The pigment of above-mentioned (2) and (3) is the material of pigment and resin formation integral body, can think similar material thus, and the present invention is suitable for using.
If making the pigment of above-mentioned (1), (2) and (3) is the ratio of components of printing ink of the present invention, then can realize the raising of drying property, high toneization especially.
Color composition as above-mentioned tinting material does not have particular restriction, can suitably select according to purpose, and for example, can be any one of mineral dye, pigment dyestuff.
As above-mentioned mineral dye, for example, can enumerate titanium oxide, ferric oxide, lime carbonate, barium sulfate, aluminium hydroxide, baryta yellow, cadmium red, chrome yellow, carbon black etc.Wherein, preferred carbon black etc.In addition, as above-mentioned carbon black, for example, can enumerate the carbon black of making by known method such as contact process, oven process, hot methods.
As above-mentioned pigment dyestuff, for example, can enumerate azo pigment, polycycle pigment, dyestuff inner complex, nitropigments, nitroso-dye, nigrosine etc.Wherein, more preferably azo pigment, polycycle pigment etc.In addition, as above-mentioned azo pigment, for example, can enumerate azo lake, insoluble azo colour, condensed azo-pigment, inner complex azo pigment etc.As above-mentioned polycycle pigment, for example, can enumerate phthalocyanine pigment, perylene dye, perylene ketone pigment, anthraquinone pigment, quinoline a word used for translation ketone pigment, two  piperazine pigment, indigo pigment, thioindigo pigment, iso-dihydro-indole pigment, Kui phthalein ketone (quinophtalone) pigment etc.As above-mentioned dyestuff inner complex, for example, can enumerate basic dye type chelates, acidic dye type chelate etc.
Color as above-mentioned pigment does not have particular restriction, can suitably select according to purpose, for example, can enumerate black with pigment, colored with pigment etc.These colors can be used a kind separately, also can use simultaneously more than 2 kinds.
As above-mentioned black pigment, for example, can enumerate metal species such as carbon black (C.I. Pigment black 7) class, copper, iron (C.I. carbon black 11), titanium oxide, nigrosine pigment dyestuffs such as (C.I Pigment blacks 1) etc. such as furnace treated black, dim, acetylene black, thermally oxidized black.
As above-mentioned colour pigment, in the Yellow ink purposes, for example can enumerate C.I. Pigment Yellow 73 1 (firm yellow G), 3,12 (dual-azo yellow AAA), 13,14,17,23,24,34,35,37,42 (Zh 1s), 53,55,74,81,83 (dual-azo yellow HR), 95,97,98,100,101,104,108,109,110,117,120,128,138,150,153 etc.
Magenta can be enumerated for example C.I. Pigment red 1 with pigment, 2,3,5,17,22 (bright firmly scarlet), 23,31,38,48:2 (permanent red 2B (Ba)), 48:2 (permanent red 2B (Ca)), 48:3 (permanent red 2B (Sr)), 48:4 (permanent red 2B (Mn)), 49:1,52:2,53:1,57:1 (brilliant carmine 6B), 60:1,63:1,63:2,64:1,81 (rhodamine 6G color lakes), 83,88,92,101 (red iron oxides), 104,105,106,108 (cadmium reds), 112,114,122 (dimethyl quinoline a word used for translation ketone), 123,146,149,166,168,170,172,177,178,179,185,190,193,209,219 etc.
Cyan pigment for example, can be enumerated C.I. pigment blue 1,2,15 (copper phthalocyanine blue R), 15:1,15:2,15:3 (phthalocyanine blue G), 15:4,15:6 (phthalocyanine blue E), 16,17:1,56,60,63 etc.
In addition, be red, green, cyan as middle shade, can enumerate C.I. Pigment red 177,194,224, C.I. pigment orange 43, C.I. pigment violet 3,19,23,37, C.I. pigment Green 7,36 etc.
If use dyestuff as above-mentioned tinting material, can obtain the printing ink of tone excellence.As above-mentioned dyestuff, for example, can enumerate water-soluble dye, oil-soluble colourant, dispersed dye etc.
As above-mentioned water-soluble dye is the dyestuff that is classified into matching stain, substantive dyestuff, basic dyestuff, chemically-reactive dyes, food dye in Colour Index, preferably uses the dyestuff water-fast, that photostabilization is excellent.
As above-mentioned matching stain and food dye, for example, can enumerate C.I. turmeric yellow 17,23,42,44,79,142; C.I. azogeramine, 8,13,14,18,26,27,35,37,42,52,82,87,89,92,97,106,111,114,115,134,186,249,254,289; C.I. acid blue 9,29,45,92,249; C.I. Acid Black 1,2,7,24,26,94; C.I. edible yellow 3,4; C.I. eat red 7,9,14; C.I. edible black 1,2 etc.
As above-mentioned substantive dyestuff, for example, can enumerate direct yellow 1,12,24,26,33,44,50,86,120,132,142,144; C.I. directly red 1,4,9,13,17,20,28,31,39,80,81,83,89,225,227; C.I. direct orange 26,29,62,102; C.I. sun blue 1,2,6,15,22,25,71,76,79,86,87,90,98,163,165,199,202; C.I. directly black 19,22,32,38,51,56,71,74,75,77,154,168,171 etc.
As above-mentioned basic dyestuff, for example, can enumerate C.I. basic yellow 1,2,11,13,14,15,19,21,23,24,25,28,29,32,36,40,41,45,49,51,53,63,64,65,67,70,73,77,87,91; C.I. alkaline red 2,12,13,14,15,18,22,23,24,27,29,35,36,38,39,46,49,51,52,54,59,68,69,70,73,78,82,102,104,109,112; C.I. alkali blue 1,3,5,7,9,21,22,26,35,41,45,47,54,62,65,66,67,69,75,77,78,89,92,93,105,117,120,122,124,129,137,141,147,155; C.I. directly black 2,8 etc.
As above-mentioned chemically-reactive dyes, for example, can enumerate C.I. reactive black 3,4,7,11,12,17; C.I. reactive yellow 1,5,11,13,14,20,21,22,25,40,47,51,55,65,67; C.I. reactive red 1,14,17,25,26,32,37,44,46,55,60,66,74,79,96,97; C.I. reactive blue 1,2,7,14,15,23,32,35,38,41,63,80,95 etc.
With respect to the total amount (for example, the total amount of resin and tinting material) of solids component, resinous principle is 40～95 quality %, is preferably 70～95 quality %.Therefore, the content of above-mentioned tinting material is preferably below the 60 quality %, more preferably below the 30 quality %.Wherein also comprise the resin of the colourant molecule with chromophoric group (for example pigment molecule) that contains in the tinting material in the resinous principle of computation process, promptly represent following implication: all the ratio of the resin total amount that comprises the colourant molecule with chromophoric group (for example pigment molecule) that contains in the tinting material in solid substance=resin+tinting material is more than the 40 quality %.
The total amount of above-mentioned solids component (total solid of resin and tinting material) is more than the 20 quality %, is preferably 20～60 quality %, more preferably 20～30 quality %.If above-mentioned solid substance amount surpasses 60 quality %, then viscosity improves, and conventional device is difficult to printing, still, by adopting the various strategies of keeping as the present invention, is not to use.But, to spread and sink in order to prevent to ooze, preferred solid substance is more.In addition, by following such making up with moistening dosage, the solid substance amount can not be too many.On the other hand, if the solids component total amount is lower than 20 quality %, moistening dosage is few, and viscosity is too low simultaneously, and image distinctiveness is poor sometimes.
But, for record, improving in order to make drying property to the low recording medium of water-retaining capacity, the moistening dosage that reduces in the recording ink is effective.Solid substance amount in the printing ink, resin ratio might not be necessary conditions when improving drying property.If the solid substance amount in the increase printing ink, because poor reliability sometimes, therefore when the little enterprising line item of recording medium of water-retaining capacity, under the situation of paying attention to drying property and reliability, can make wetting agent amount (perhaps being the one-tenth component of liquid down at 25 ℃) is below the 20 quality %, and the solid substance amount rests near the 10 quality %.In addition, in order to improve drying property, making moistening dosage is to be more effective below the 10 quality %.
As above-mentioned other compositions, there is not particular restriction, can suitably select as required, for example, can enumerate defoamer, Antisepticize and mildew preventive, rust-preventive agent, pH regulator agent, resistivity regulator, antioxidant, UV light absorber, oxygen absorbent, photostabilizer, viscosity modifier etc.
As above-mentioned defoamer, there is not particular restriction, can suitably select according to purpose, for example, can suitably enumerate silicone based defoamer, polyethers defoamer, fatty acid ester defoamer etc.These materials can use a kind separately, also can use simultaneously more than 2 kinds.Wherein, from the viewpoint of defoaming effect excellence, preferred organic silicon defoamer.
As above-mentioned silicone based defoamer, for example, can enumerate oil type silicone antifoam agent, compound silicone antifoam agent, self-emulsifying type silicone antifoam agent, latex organosilicon defoamer, modified organic silicon defoamer etc.As this modified organic silicon defoamer, for example, can enumerate amino-modified silicone defoamer, Trivalin SF modified organic silicon defoamer, methacrylic acid modified organic silicon defoamer, organic silicon modified by polyether defoamer, alkyl-modified silicone based defoamer, high-grade aliphatic ester modified organic silicon defoamer, epoxy alkane modified organic silicon defoamer etc.Wherein, if consideration is used for the above-mentioned recording ink as water-medium, the silicone based defoamer of preferred above-mentioned self-emulsifying type, the silicone based defoamer of above-mentioned emulsion type etc.
As above-mentioned defoamer, can also use commercially available product, as this commercially available product, can enumerate the silicone based defoamer (SAG30 etc.) that silicone based defoamer (KS508, KS531, KM72, KM85 etc.) that Shin-Etsu Chemial Co., Ltd makes, silicone antifoam agent (Q2-3183A, SH5510 etc.) that eastern レ ダ ウ コ one ニ Application グ Co., Ltd. makes, Japanese ユ ニ カ one Co., Ltd. make, the defoamer (ア デ カ ネ one ト series etc.) that Asahi Denka Kogyo K. K makes etc.
As the content of above-mentioned defoamer in above-mentioned recording ink, there is not particular restriction, can suitably select according to purpose, for example, be preferably 0.001～3 quality %, more preferably 0.05～0.5 quality %.
As above-mentioned Antisepticize and mildew preventive, for example, can enumerate 1,2-benzisothiazole-3-ketone, Sodium dehydroacetate, sodium sorbate, 2-pyridine mercaptan-1-sodium oxide, Sodium Benzoate, sodium pentachlorophenol etc.
As above-mentioned resistivity regulator, can be by containing inorganic salts, for example, alkali metal halide or ammonium halide (for example lithium chloride, ammonium chloride, sodium-chlor) etc. and record liquid that preparation is used in the ink jet recording method that makes the charged type of recording ink.
As above-mentioned pH regulator agent, so long as the recording ink that is mixed is not being brought under the dysgenic situation, with the material of pH regulator to expected value, just there is not particular restriction, can suitably select according to purpose, for example, can enumerate alcamines, alkali metal hydroxide, ammonium oxyhydroxide, Phosphonium oxyhydroxide, alkaline carbonate etc.
As above-mentioned alcamines, for example, can enumerate diethanolamine, trolamine, 2-amino-2-ethyl-1, ammediol etc.
As the oxyhydroxide of above-mentioned alkali metal, for example, can enumerate lithium hydroxide, sodium hydroxide, potassium hydroxide etc.
As the oxyhydroxide of above-mentioned ammonium, for example, can enumerate ammonium hydroxide, quaternary ammonium hydroxide, quaternary phosphine oxyhydroxide etc.
As above-mentioned alkali-metal carbonate, for example, can enumerate Quilonum Retard, yellow soda ash, salt of wormwood etc.
As above-mentioned rust-preventive agent, for example, can enumerate acid accumulator sulfite, Sulfothiorine, thiodiglycolic acid ammonium, di-isopropyl ammonium nitrate, four pentaerythritol tetranitrates, dicyclohexyl ammonium nitrate etc.
As above-mentioned antioxidant, for example, can enumerate phenol antioxidant (comprising hindered phenol anti-oxidants), amine antioxidants, sulphur class antioxidant, Phosphorus antioxidant etc.
As above-mentioned phenol antioxidant (comprising hindered phenol anti-oxidants); for example; can enumerate butylated hydroxy anisole (BHA); 2; 6-di-t-butyl-4-ethylphenol; stearyl--β-(3,5-di-t-butyl-4-hydroxyphenyl) propionic ester; 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol); 2; 2 '-methylene-bis(4-ethyl-6-t-butyl phenol); 4; 4 '-Ding pitches (3 methy 6 tert butyl phenol); 3, two [1,1-dimethyl-2-[β-(3-tertiary butyl-4-hydroxy-5-tolyl) propionyloxy] ethyls of 9-]-2; 4; 8,10-four spiral shells [5,5] undecane; 1; 1; 3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane; 1,3,5-trimethylammonium-2; 4; 6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene; four [methylene radical-3-(3 ', 5 '-di-t-butyl-4 '-hydroxyphenyl) propionic ester] methane etc.
As above-mentioned amine antioxidants, for example, can enumerate Phenyl beta naphthylamine, alpha-naphthylamine, N, N '-di-sec-butyl-p-phenyl enediamine, phenothiazine, N, N '-diphenyl-para-phenylene diamine, 2, the 6-ditertbutylparacresol, 2, the 6-DI-tert-butylphenol compounds, 2,4-dimethyl-6-tert.-butyl phenol, butyl hydroxyanisole, 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol), 4,4 '-Ding fork two (3 methy 6 tert butyl phenol), 4,4 '-thiobis (3 methy 6 tert butyl phenol), four [methylene radical-3-(3,5-di-t-butyl-4-dihydroxyphenyl) propionic ester] methane, 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane etc.
As above-mentioned sulphur class antioxidant, for example, can enumerate dilauryl 3,3 '-thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, myristyl 3,3 '-thiodipropionate, distearyl β, β '-thiodipropionate, 2-mercaptobenzimidazole, dilauryl sulfoxide etc.
As above-mentioned Phosphorus antioxidant, can enumerate triphenyl phosphite, phosphorous acid stearyl, tricresyl phosphite isodecyl ester, trilauryl trithiophosphite, Wytox 312 etc.
As above-mentioned UV light absorber, for example, can enumerate benzophenone UV light absorber, benzotriazole category UV light absorber, salicylate class UV light absorber, cyanoacrylate UV light absorber, nickel complexing salt UV light absorber etc.
As above-mentioned benzophenone UV light absorber, for example, can enumerate Octabenzone, 2-hydroxyl-4-positive 12-alkoxy benzophenone, 2,4-dihydroxy benaophenonel, 2-hydroxyl-4-methoxy benzophenone, 2,2 ', 4,4 '-tetrahydroxybenzophenone etc.
As above-mentioned benzotriazole category ultraviolet-resistant absorbent, for example, can enumerate 2-(2 '-hydroxyl-5 '-uncle's octyl phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-4 '-octyloxyphenyl) benzotriazole, 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorobenzotriazole etc.
As above-mentioned salicylic acid UV light absorber, for example, can enumerate salol, to tert-butyl-phenyl salicylate, p-octylphenyl salicylate etc.
As above-mentioned cyanoacrylate UV light absorber, for example, can enumerate ethyl-2-cyano group-3,3 '-diphenylacrylate ester, methyl-2-cyano group-3-methyl-3-(p-methoxyphenyl) acrylate, butyl-2-cyano group-3-methyl-3-(p-methoxyphenyl) acrylate etc.
As above-mentioned nickel complexing salt UV light absorber, for example, can enumerate two (octyl phenyl) nickelous sulfides, 2,2 '-thiobis (uncle's 4-octyl group benzoic ether (Off エ レ one ト)) n-butylamine nickel (II), 2,2 '-thiobis (uncle's 4-octyl group benzoic ether)-2-DEHA nickel (II), 2,2 '-thiobis (uncle's 4-octyl group benzoic ether) trolamine nickel (II) etc.
Recording ink of the present invention is to contain tinting material and resin and be that solid solid state component, boiling point are higher and be the liquid component of liquid and water and other compositions of using as required under 25 ℃ than water under 25 ℃ by dispersing or dissolving in aqueous medium, and mixes as required and make.In general, tinting material, resin use the material that is dissolved or dispersed in advance in the water.Above-mentioned dispersion for example adopts that sand mill, homogenizer, ball mill, coating vibrator, ultrasonic dispersing machine etc. carry out, and mixes to utilize the stirrer that uses common paddle, magnetic stirrer, high speed dispersor etc. to carry out.
Rerum natura as recording ink of the present invention does not have particular restriction, can suitably select according to purpose, and for example, preferred viscosities, surface tension, pH etc. are in following scope.
The viscosity of above-mentioned recording ink is down below the 20mPas, more preferably below the 15mpas at preferred 25 ℃.If above-mentioned viscosity greater than 25mpas, is difficult to guarantee jetting stability.But, depending on nozzle structure, may not use.
As the surface tension of above-mentioned recording ink, preferably be 35mN/m down, more preferably below the 30mN/m at 25 ℃.In addition, be preferably more than the 15mN/m, more preferably more than the 20mN/m.If above-mentioned surface tension greater than 35mN/m, then is difficult to cause the levelling of the printing ink on the recording medium, cause the prolongation of time of drying.On the other hand, if above-mentioned surface tension is too low, the infiltration of the printing ink on nozzle face is strong excessively, and it is unstable that the formation of meniscus becomes, and causes that sometimes ejection is bad.
Above-mentioned surface tension for example can utilize full-automatic tensiometer (CBVP-Z, consonance interface science Co., Ltd. makes) to measure.
As the pH of above-mentioned recording ink, for example, be preferably 7～10.
Painted as recording ink of the present invention do not have particular restriction, can suitably select according to purpose, can enumerate yellow, magenta, cyan, black etc.Used more than 2 kinds these painted printing ink groups to carry out record simultaneously if use, then can write down multicolor image,, then can write down full-colour image if use the printing ink group of having used all colours simultaneously.
Recording ink of the present invention can be applied to carry ink gun arbitrarily as described below printer as ink gun well: utilize piezoelectric element to make the vibrating plate distortion that forms the oil ink passage wall as the living pressure device that the printing ink in the oil ink passage is pressurizeed, thereby the oil ink passage internal volume is changed and the so-called piezo-electric type ink gun (opening flat 2-51734 communique) of discharging droplets of ink with reference to the spy, perhaps utilize heating resistor, the so-called pattern of fever ink gun (opening clear 61-59911 communique) that in oil ink passage, printing ink is added the thermogenesis bubble with reference to the spy, be oppositely arranged the vibrating plate and the electrode that form the oil ink passage wall, make vibrating plate distortion by the electrostatic force that between vibrating plate and electrode, produces, thereby make the oil ink passage volume-variation and discharge the so-called electrostatic ink gun (opening flat 6-71882 communique) etc. of droplets of ink with reference to the spy.
Recording ink of the present invention can be applicable to various fields, go for adopting the image recording structure (printer etc.) of ink-jet recording, for example, can also be applied to have the printer of function as described below etc.: before and after printing or printing 50～200 ℃ down heating be recorded with paper and above-mentioned recording ink and promote to print photographic fixing, be specially adapted to following print cartridge of the present invention, ink recorded matter, ink-jet recording device, ink jet recording method.
(print cartridge)
The recording ink that print cartridge of the present invention holds in container in recording ink of the present invention or the ink medium group of the present invention constitutes, and has the miscellaneous part of suitable selection as required etc. in addition.
As said vesse, there is not particular restriction, can suitably select its shape, structure, size, material etc. according to purpose, for example, can suitably enumerate and have containers such as Printing ink bag that form by aluminium lamination press mold, resin molding etc. etc. at least.
Below with reference to Fig. 1 and Fig. 2 print cartridge is described.Wherein, Fig. 1 is the figure of an example of expression print cartridge of the present invention, and Fig. 2 is the figure of the shell (housing) that also comprises print cartridge.
As shown in Figure 1, print cartridge is to be filled in the Printing ink bag 41 from printing ink inlet 42, and after the exhaust, this printing ink inlet 42 is closed by melt bonded.In use, the ink emission mouth 43 that being needled into of apparatus main body is made of rubber components and being supplied in the device.
Utilization does not have the package members such as aluminium lamination press mold of ventilation property to form Printing ink bag 41.As shown in Figure 2, this Printing ink bag 41 is contained in the plastics system print cartridge shell 44 usually, and can removably be mounted in the various ink-jet recording device.
(ink-jet recording device and ink jet recording method)
Ink-jet recording device of the present invention has the printing ink flight instruments at least, also has other devices of suitable selection as required, for example stimulates generation device, control device etc.
Ink jet recording method of the present invention comprises printing ink flight operation at least, also comprises other operations of suitable selection as required, for example, stimulates to produce operation, control operation etc.
Ink jet recording method of the present invention can utilize ink-jet recording device of the present invention suitably to carry out, and above-mentioned printing ink flight operation can utilize above-mentioned printing ink flight instruments suitably to carry out.In addition, above-mentioned other operations can suitably be carried out by above-mentioned other devices.
-printing ink flight operation and printing ink flight instruments-
Above-mentioned printing ink flight operation is that recording ink of the invention described above or the recording ink in the ink medium group of the present invention are applied stimulation, makes above-mentioned recording ink flight and the operation of formation image.
Above-mentioned printing ink flight instruments is that the recording ink in recording ink of the invention described above or the ink medium group of the present invention is applied stimulation, makes this recording ink flight and the device of formation image.As this printing ink flight instruments, there is not particular restriction, can suitably select according to purpose, for example, can enumerate various record-headers (ink jet head), especially preferably have the record-header that contains a plurality of nozzle rows and hold by the liquid of liquid keeping groove supply and liquid is supplied to the flight instruments of the pilot trench of above-mentioned record-header.
Above-mentioned pilot trench preferably has in this pilot trench the negative pressure generation device that produces negative pressure, in this pilot trench open atmosphere the atmosphere opening device and utilize resistance difference to detect the proofing unit that whether has printing ink.
Above-mentioned stimulation for example can produce by above-mentioned stimulation generation device, as this stimulation, does not have particular restriction, can suitably select according to purpose, can enumerate heat (temperature), pressure, vibration, light etc.These can use a kind separately, also can use simultaneously more than 2 kinds.Wherein, preferably enumerate heat, pressure.
In addition, as above-mentioned stimulation generation device, for example, can enumerate heating unit, pressurizing device, piezoelectric element, vibration generating arrangement, ultrasonic oscillator, lamp etc.Particularly, can enumerate piezoelectric driving systen such as piezoelectric element, use electrothermal conversioning element such as heating resistor and utilize the phase transformation that the film boiling by liquid causes thermal actuator, utilize the metal phase change that causes by temperature variation shape memory alloy actuator, utilize the electrostatic actuator of electrostatic force etc.
Flying method as above-mentioned recording ink, there is not particular restriction, according to above-mentioned stimulation kind etc. and different, for example, when above-mentioned stimulation is " heat ", can be listed below method etc.: utilize for example hot first-class above-mentioned recording ink in record-header to give and the corresponding heat energy of recording signal, make above-mentioned recording ink produce bubble by this heat energy, by the pressure of this bubble, spray the method for this recording ink of discharge with the drop form from the nozzle bore of this record-header.In addition, when above-mentioned stimulation is " pressure ", for example, can be listed below method etc.: apply voltage by piezoelectric element to the position that is called as the pressure chamber that adheres to the oil ink passage that is positioned at record-header, the piezoelectric element bending, the volume of pressure chamber dwindles, and sprays the method for this recording ink of discharge with the drop form from the nozzle bore of this record-header.
Preferably apply the method that voltage makes recording ink flight to piezoelectric element.Because the piezoelectricity mode is not generated heat, thereby helping making the printing ink flight that contains resin, under the situation of the poor printing ink that uses wetting agent, is the effective ways that make spray nozzle clogging few especially.
In addition, in order to prevent spray nozzle clogging, preferably piezoelectric element is applied the forceful electric power of not discharging printing ink and compress into line space and scan in vain.In addition, preferably before the blank scanning of finishing 1 page of printing, carry out operation to printing ink reservoir ejection printing ink.
In addition, preferably has the removing device that strikes off the printing ink that adheres to empty injection susceptor (empty jet support).As this removing device, any one of preferred curette (wiper) and scraper plate.
When using the such few recording ink of moistening dosage of the present invention, when forming ink jet image, as the method for eliminating plug nozzle, preferably when stopping using for a long time more than 1 day (when not carrying out ink-vapor recording), with near the printing ink the alternative record-header nozzle of moisture retention liquid, when restarting ink-vapor recording, substitute this moisture retention liquid with printing ink of the present invention and carry out image formation afterwards.
When stopping using for a long time,, can prevent the sealing evaporation and spray nozzle clogging that tinting material and resin dehydration are caused like this by utilizing moisture retention liquid to substitute near the nozzle printing ink.In addition, when restarting ink-vapor recording, carry out image formation, can form high-density images by utilizing recording ink of the present invention to substitute moisture retention liquid.
As above-mentioned moisture retention liquid, can be water, can also be the water (can also contain other minor amounts of additives, pH regulator agent, tensio-active agent etc.) that contains wetting agent.So long as compare with recording ink of the present invention is the strong solution of obstruction that anti-sealing evaporation causes, and mix with recording ink of the present invention solid precipitation do not take place yet, can also redispersion or the liquid of removing the dry bur of recording ink of the present invention get final product.That is, be the water or the aqueous solution that contains wetting agent, perhaps moisture, wetting agent, tinting material, resin etc. and under 25 ℃, be the liquid of solid-state solids component few (or not having fully).When especially on being difficult to exsiccant hectograph White Board, printing, can utilize the few printing ink of wetting agent to print, when stopping using,, then can prevent to stop up if utilize moisture retention liquid to substitute near the recording ink of nozzle.
As above-mentioned moisture retention liquid, be preferably (1) and wrap that liquid medium, (3) that aqueous liquid medium, (2) are main component with water are higher than water with water and boiling point and be that liquid medium and (4) of main component comprise the composition identical with above-mentioned recording ink and are down in the liquid medium that lacks than this recording ink of the content of solid solids component any at 25 ℃ under 25 ℃ at the liquid component that is liquid.The recording ink of above-mentioned (4) is the type that is used in usually in the ink-vapor recording.
Here, so-called is that main component is meant the water that contains more than the 90 quality % with water.
In addition, so-calledly be higher than water and be that main component is meant and contains water and boiling point is higher than water and be 90 quality %s more than in the total amount that is the liquid component of liquid under 25 ℃ under 25 ℃ at the liquid component that is liquid with water and boiling point.
In addition, as with the identical composition of above-mentioned recording ink of the present invention, can also be to increase moistening dosage with respect to recording ink, reduce the liquid of solid substances such as tinting material on the contrary.At this moment, moisture retention liquid itself can also be used as lower concentration colorant inks, promptly so-called light concentration printing ink.
Above-mentioned moisture retention liquid is preferably kept in the groove different with recording ink, and is supplied to the nozzle position before stopping using for a long time.At this moment, can be the method for exchange black groove itself, the liquid bath of preserving moisture can also for good and all be set, and setting and recording ink are with the different passage that moisture retention liquid is supplied to nozzle of passage.But these methods are the technology that ideally prevents spray nozzle clogging after all, after stopping using, even some obstructions are arranged, also can recover by removing, therefore, also can use recording ink of the present invention even without moisture retention liquid.
In addition, when utilizing the few recording ink of the such moistening dosage of the present invention to form ink jet image,, there is employing that the method for the device of water is provided to the cladding system (lid of preserving moisture) at the nozzle position that covers record-header as the method for eliminating spray nozzle clogging.
In general, because the equilibrium water component height of wetting agent, the evaporation of moisture slows down, and has that the printing ink of delaying solidifies, the exsiccant effect.On the other hand, the printing ink that contains the lower concentration wetting agent that the present invention is such, this effect is low.Therefore,, make and preserve moisture the interior humidity of lid at least,, also can suppress the spray nozzle clogging that causes by drying even the moistening dosage of printing ink is few near 100% if in the lid of preserving moisture, provide water.As the method for supplied water, it is main component with water that other preparation keeping is arranged, and has the box of the liquid of a spot of pH regulator agent, Antisepticize and mildew preventive, sprays the method for supplied water in lid by methods such as nozzle printings.Liquid as supply in lid except water, can also use above-mentioned all moisture retention liquids of enumerating, but preferred wetting agent or solid substance are few, and the many liquid of water.When more preferably additionally preparing nozzle segment is carried out the few liquid of the moisture retention liquid of fluid exchange different washiness, solid substance as the liquid of supplying in lid with long-term the placement.
The countermeasure that adopts above-mentioned moisture retention liquid and obtain to improve reliability is not limited to use the situation of above-mentioned recording ink of the present invention, common pigment ink is at least for situation that might cause reliability to reduce also is effective because nozzle is dry, but particularly, as above-mentioned recording ink of the present invention, be more effective under the situation of the danger few at moistening dosage, that the reliability reduction is arranged.
In addition, be 2mm at area 2When printing on the area of above part on the spot, by at every printing 2mm 2In the when and where printing of staggering, can eliminate the difference of position image color on the spot.
In addition, preferably use non-porous base materials such as plastics film, plastic layer platen, plastic coated paper, glass, metal, behind the enterprising line item of this porous substrate, make this document image drying by at least a method in heating and the air-supply as recording medium.
In addition,,, just do not have particular restriction, can suitably select, for example, can enumerate instruments such as programunit, computer according to purpose as long as can control the running of above-mentioned each device as above-mentioned control device.
In the present invention, preferably on discharging plate face with peristome, the printing ink that has formed the ink gun that makes printing ink flight has anti-ink lay.
The surfaceness of the anti-ink lay that uses among the present invention (Ra) is preferably below the 0.2 μ m.By making surface roughness Ra is that the wiping in the time of can reducing friction contact is residual below the 0.2 μ m.
Figure 22 and Figure 23 A～Figure 23 C are the sectional views of the nozzle plate of the ink gun that uses among the present invention.
In the present embodiment, nozzle plate 32 as the plate substrate of ink gun is made by the electroforming (electroform) of Ni, its surface forms anti-ink lay 31, should anti-ink lay 31 be the above silicone resin epitheliums of thickness 1  (0.1nm), and its surfaceness be preferably below the Ra=0.2 μ m.In addition, the thickness of anti-ink lay 31 is preferably more than the 0.1 μ m, more preferably more than the 0.5 μ m.
When filling printing ink 3, shown in Figure 23 C, form meniscus (liquid level) P at the boundary member of anti-ink lay 31 that forms by the silicone resin epithelium and nozzle plate 32.
Be formed on offering of ink gun printing ink discharge waterproof layer on the plate face of peristome (nozzle) of usefulness when forming, make to be positioned at sectional area perpendicular to the anti-ink lay on the plane of the medullary ray of this peristome along with increasing gradually near this peristome away from the plate substrate surface.
Near the peristome of above-mentioned anti-ink lay shape is preferably curve form.In addition, in the planar cross section of the medullary ray that comprises above-mentioned peristome, near the radius-of-curvature of the curve this peristome of anti-ink lay is preferably more than the thickness of this anti-ink lay.
In addition, in the planar cross section of the medullary ray that comprises above-mentioned peristome, be the roughly curve of circular arc from this peristome edge of preventing ink lay near the curve this peristome, the radius-of-curvature of this circular arc is preferably more than the thickness of this anti-ink lay.
In addition, in the planar cross section of the medullary ray that comprises above-mentioned peristome, the tangent line at this peristome edge by anti-ink lay and the jet element surface angulation that comprises this end are preferably less than 90 degree.
When offering the peristome of nozzle plate 32, it is the circular at center that the planar cross section of the medullary ray of representing perpendicular to the long and short dash line among Figure 23 A～Figure 23 C is become with this medullary ray.In addition, be formed on anti-ink lay 31 on the printing ink discharge face in the nozzle plate 32 when forming, make sectional area perpendicular to the opening portion in the plane of this medullary ray along with increasing gradually away from nozzle plate 32.
In more detail, shown in Figure 23 A, the opening portion of anti-ink lay 31 is the circle that radius-of-curvature is r from the peristome edge of nozzle plate 32 near the curve the peristome.This radius-of-curvature r is preferably more than near the thickness d in addition of opening portion of waterproof layer 31.
This thickness d is the thickness as the part beyond the circular portion of the opening portion of anti-ink lay 31, can be preferably the maximum ga(u)ge of anti-ink lay.
Like this, the opening portion of the anti-ink lay 31 that is connected with the peristome of nozzle plate 32 is the shapes (the level and smooth curve that does not have pointed part) that do not have pointed end, owing to obtain not having the curve of crotch part (hookedportion), when promptly using the curette friction contact of making by materials such as rubber, also can not produce pointed hook segment on curette and make anti-ink lay 31 peel off such unfavorable condition from nozzle plate 32.
In addition, shown in Figure 23 B, in the planar cross section of the medullary ray of the peristome that comprises nozzle plate 32, the tangent line at the peristome edge by anti-ink lay 31 and the nozzle plate 32 surperficial angulation θ at the peristome edge that comprises the nozzle plate 32 that is connected this opening portion are preferably less than 90 degree.
Because the tangent line at the opening portion edge of anti-ink lay 31 and the angle θ of nozzle plate surface 32 are less than 90 degree, therefore, shown in Figure 23 C, boundary member at anti-ink lay 31 and nozzle plate 32 stably forms meniscus (liquid level) P, and can reduce to form in other parts the possibility of meniscus P greatly.As a result, owing to can stably form meniscus, in the image processing system that has used the ink gun that comprises nozzle plate 32, the jetting stability of printing ink is good when carrying out image formation.
As the silicone resin that uses in the present embodiment, the silicone resin of the liquid state of preferred room temperature curing type is more preferably with the silicone resin of hydrolysis reaction.In embodiment described later, the SR2411 that Shi Yong East レ ダ ウ コ one ニ Application グ Co., Ltd. makes.
Following Table A be about the peristome edge of the nozzle plate 32 in the anti-ink lay 31 in the ink gun in the present embodiment to the printing ink around near the shape the peristome edge, the nozzle accumulate, the edge is peeled off, the evaluation result of jetting stability.
Table A
Edge shape Printing ink accumulates The edge is peeled off Jetting stability
Sharp-pointed end is arranged Part takes place Take place Well
No sharp-pointed end (round-shaped) θ≤90° Do not have Do not have Well
θ＞90° Do not have Do not have Bad
r≥d Do not have Do not have Well
r＜d Do not have Part takes place Bad
By the result of Table A as can be known, contain a little at the edge part () of anti-ink lay 31 that the ink gun of the shape of pointed end accumulates at nozzle found around printing ink, and generation is peeled off because of the edge that friction contact causes at opening portion the edge near.
Do not accumulate though printing ink does not take place round-shaped ink gun, as a comparison, the ink gun generation part edge of the r＜d shown in Figure 24 A is peeled off, and the ink gun of the θ shown in Figure 24 B＞90 degree is unsettled results of injection of drop.
In addition, shown in Figure 24 C, the ink gun of the ink gun of r＜d or θ＞90 degree is when filling printing ink, the situation that forms meniscus (liquid level) P at the boundary member of anti-ink lay 31 and nozzle plate 32 is arranged, and in the situation that forms meniscus Q towards the protuberance at the opening portion center of anti-ink lay 31 ' (perpendicular to the part of the sectional area minimum of the medullary ray of opening portion).Therefore, when adopting the ink-jet recording device that has used the ink gun that contains nozzle plate 32 to carry out image recording, produce the uneven situation of jetting stability of printing ink sometimes.
Then, the manufacture method of the jet element of the ink gun that above-mentioned present embodiment is related to describes.
Shown in Figure 25 is coating by the dispenser 34 (dispenser) that uses present embodiment, silicone-coating and form the figure of the structure of anti-ink lay 31.
Be provided for discharging the dispenser 34 of face one side coating organic silicon solution at the printing ink of the nozzle 32 that adopts the Ni electroforming to form, the interval that nozzle plate 32 and needle roller (needle) 35 front ends keep predetermined certain distance, discharge organosilicon scan edge dispenser 34 from needle roller 35 front end edge, like this, shown in above-mentioned Figure 22 and Figure 23 A～Figure 23 C, can optionally form the silicone resin epithelium at the printing ink of nozzle plate 32 face of discharging.
The silicone resin that uses in the present embodiment uses normal temperature cured type silicone resin SR2411 (East レ ダ ウ コ one ニ Application グ Co., Ltd. to make viscosity: 10mPas).But, find to have spread some organosilicons at nozzle bore and nozzle plate inner face.So optionally the thickness of the silicone resin epithelium of Xing Chenging is 1.2 μ m, and surfaceness (Ra) is 0.18 μ m.
Shown in Figure 26 A, the coating mouth of needle roller 35 front ends that present embodiment relates to is guaranteed to be coated with the coating width that requires to 32 of nozzle plates as the coating object.Thus, on the coating direction,, just can finish coating to whole coating object only to dispenser 34 scannings 1 time.
That is, the scanning direction that is used to be coated with operation can only be a direction, can change direction as Figure 26 B or scan opposite direction.
Therefore, shown in Figure 26 B, the front end of common needle roller 35 is because more than narrow and small as the coating width of the nozzle plate 32 that is coated with object, therefore, in order to finish coating to whole coating object, be necessary that scanning direction change 90 degree that use and be coated with operation move, thereby perhaps therefore scanning in the opposite direction be difficult to homogeneous thickness whole coating object is coated with in multi-direction scanning.
According to present embodiment,, process thereby can be used as the precision surface of good because the width of the coating mouth of needle roller 35 front ends has been guaranteed therefore can make the coating thickness of whole coating object even to the coating width as the nozzle plate 32 that is coated with object.
The figure of the coating operation that is to use the dispenser 34 that present embodiment relates to shown in Figure 27.Its basic structure is identical with Figure 25, and the limit is from nozzle bore (peristome) the jet flow stream 36 limits coating organosilicon of nozzle plate 32.As this gas 36,, for example can be air so long as the gas of the organosilicon generation chemical reaction of difficult and coating then can use all gases.
Like this, be coated with from nozzle bore jet flow stream 36 limits, can only form the silicone resin epithelium at the nozzle surface except the nozzle bore of nozzle plate 32 by the limit.
In addition, if use same silicone resin to be coated with but jet flow stream 36 not, after organic silicone resin enters into predetermined depth, again from nozzle 32 jet flow stream 36, then as shown in figure 28, can form the degree of depth (about for example a few μ ms) of the anti-ink lay of silicone resin up to the expectation of nozzle inner walls.That is, except above-mentioned printing ink is discharged the anti-ink lay 31 of face, also can form as thin as a wafer anti-ink lay 31a (the anti-ink lay of peristome inwall) up to the predetermined degree of depth at the peristome edge of nozzle plate 32.
For the anti-ink lay 31 of the nozzle plate of such making, use EPDM rubber (rubber hardness 50 degree) to implement friction contact.As a result, even carry out friction contact 1000 times, the anti-ink lay 31 of nozzle plate also can be kept good anti-printing ink.In addition, with the jet element that formed anti-ink lay dip treating 14 days in 70 ℃ printing ink.As a result, also can keep the anti-printing ink that does not change with the initial stage thereafter.
Shown in Figure 29 is the figure of an example of ink gun of the present invention, and expression is processed to form the state of nozzle bore with excimer laser.Nozzle plate 43 is engaged resin component 121 and high rigid element 125 by thermoplastic adhesive 126, and the surface of resin component 121 lamination successively forms SiO 2 Thin film layer 122 and fluorine class waterproof layer 123, the nozzle bore 44 of the required diameter of formation on resin component 121 forms the nozzle connected entrance 127 that is communicated with nozzle bore 44 on high rigid element 125.SiO 2The formation of thin film layer 122 is little with the relation of heat, that is, the temperature of the scope of the influence that resin component is not taken place heat with can be film forming method form.Particularly, preferred sputter, ionic fluid evaporation, ion plating, CVD (chemical vapor deposition method), P-CVD (plasma body vapour deposition method) etc.
On engineering time, materials cost, SiO 2The necessary minimal thickness of the thickness of thin film layer 122 under the scope that can guarantee bounding force is favourable.This is because if this thickness is too thick, sometimes the nozzle bore processing of adopting excimer laser is brought obstruction.That is, even resin component 121 fitly is processed into nozzle bore shape, SiO 2The part of thin film layer 122 can not fully be processed, and exists processing residual sometimes.Therefore, particularly, as can guaranteeing bounding force, and add residual Si O not in man-hour in excimer laser 2The scope of thin film layer 122, (it is suitable that 0.1～30nm) scope can be described as for thickness 1 ～300 .It more suitably is 10 ～100  (scope of 1～10nm).Experimental result, SiO 2When thickness was 30  (3nm), binding property is fully, and was no problem fully for the processibility that adopts excimer laser.In addition, during 300  (30nm), though it is residual to observe a spot of processing, operable scope, if surpass 300  (30nm), it is residual then to produce sizable processing, can see can not usage degree special-shaped nozzle.
The material of above-mentioned anti-ink lay particularly, can be enumerated fluorine class water-proof material, silicone based water-proof material so long as the material of anti-printing ink can use.
For above-mentioned fluorine class water-proof material, known have various materials, here, ((ダ イ キ Application industrial makes the mixture of the perfluor polyoxy heterocycle butane of 0.1～3nm) thickness and modification perfluor polyoxy heterocycle butane by evaporation 1 ～30 , trade(brand)name: オ プ Star one Le DSX), obtain necessary water-repellancy.Experimental result when the thickness of オ プ Star one Le DSX is 10 , 20 , 30 , is not found difference for water-repellancy, friction contact endurance quality.Therefore, consider from the cost aspect, more preferably 1 ～20  (0.1～2nm).But according to the printing ink that uses, from the viewpoint of reliability, what thickened waterproof membrane thickness can keep performance for more time, therefore, in this case, preferred 100 ～200  (10～20nm) thickness.In addition, attach self adhesive tape 124 on the surface of fluorine class waterproof layer 123, this self adhesive tape has been coated with jointing material on resinous film, and its performance excimer laser adds the subsidiary function in man-hour.In addition, can also use silicone based water-proof material.
As above-mentioned silicone based water-proof material preferably the liquid silicone resin or the elastomerics of room temperature curing type, it is coated on substrate surface, by at room temperature being placed in the atmosphere and polymerizing curable, thereby forms the epithelium of anti-printing ink.
Liquid silicone resin or elastomerics that above-mentioned silicone based water-proof material can also be a heat-curing type, it is coated on substrate surface, solidifies by heat treated, thereby forms the epithelium of preventing printing ink.
Silicone based water-proof material can also be the liquid silicone resin or the elastomerics of ultraviolet hardening, and it is coated on substrate surface, solidifies by irradiation ultraviolet radiation, thereby forms the epithelium of preventing printing ink.
The viscosity of silicone based water-proof material is preferably below the 1000cp (centipoise).
Shown in Figure 30 be the working nozzle hole time Excimer Laser Processing Equipment for Chemical Vapor Deposition that uses the figure of structure, the excimer laser beam that penetrates from laser oscillator 81 mirror 83,85,88 reflections that are reflected import on the machine table 90.Arrive in the light path of machine table 90 at laser beam 82, arrive machining object, optical beam expander 84, mask 86, field lens 87, imaging optical system 89 are set in the position of regulation in order to make only light beam.Machining object (nozzle plate) 91 is placed on the machine table 90, accepts laser beam.Machine table 90 is made of well-known XYZ platform etc., and as required, mobile machining object 91 makes laser can shine the position of expectation.Here, utilize excimer laser to be illustrated, but laser then can utilize various laser so long as can melt the short wavelength's of processing ultraviolet laser.
Figure 31 A～Figure 31 E be pattern the figure of the nozzle plate manufacturing process in the manufacture method of ink gun of the present invention is shown.
Figure 31 A shows the material that forms the base material of parts as nozzle,, as resin molding 121, for example uses the film of no particle of the power プ ト Application (trade(brand)name) of the polyimide film that E.I.Du Pont Company makes here.Consider that from the operability (sliding) on cylinder film (roll film) treatment unit common polyimide film has added SiO in mould material 2Particles such as (silicon-dioxide).Carry out nozzle bore with excimer laser and add man-hour, because SiO 2The excimer laser poor in processability of (silicon-dioxide) particle produces special-shaped nozzle sometimes.Therefore, in the present invention, use and do not add SiO 2The film of (silicon-dioxide) particle.In addition, as the plate substrate material, can use the emerging ユ one ピ レ Star Network ス that makes that produces of space portion as polyimide film.The particle of ユ one ピ レ Star Network ス is very fine, can not produce obstacle man-hour adding, and therefore can directly use.
Shown in Figure 31 B is to form SiO on the surface of resin molding 121 2The figure of the operation of thin film layer 122.This SiO 2The formation of thin film layer 122 is adapted at the sputtering method that carries out in the vacuum chamber, and thickness is preferably 1 ～300  (about 0.1～30nm).Here, form 10 ～100  (thickness of 1～10nm).As the method for sputter, behind the use sputter Si, by making O 2Ion contacts with the Si surface and forms SiO 2During the method for film, can improve SiO 2The bounding force of the resin molding 121 of film can obtain even and fine and close film simultaneously, and is more effective for the friction contact weather resistance that improves waterproof membrane.
Shown in Figure 31 C is the figure of the operation of coating fluorine class water-resisting agent 123a.As coating process, can use methods such as spin coating, roller coat, silk screen printing, spraying, but carry out film forming method owing to be related to the binding property raising that makes waterproof membrane with vacuum evaporation, therefore more effective.In addition, the SiO of this vacuum evaporation in forming Figure 31 B 2Behind the thin film layer 122, directly in vacuum chamber, implement, then can obtain better effect.Think and forming SiO in the past 2Behind the thin film layer 122, from vacuum chamber, take out workpiece, therefore, owing to impurity etc. makes binding property impaired attached to the surface.In addition, for fluorine class water-proof material, known have various materials, but, by using perfluor polyoxy heterocycle butane, modification perfluor polyoxy heterocycle butane or both mixtures as the noncrystalline compound of fluorine, can obtain the water-repellancy to necessity of printing ink here." オ プ Star one Le DSX " that above-mentioned ダ イ キ Application industrial makes is also sometimes referred to as " the terminal-modified PFPE of organoalkoxysilane ".
Shown in Figure 31 D is the figure of the aerial placement operation behind the waterproof membrane evaporation.By this operation, fluorine class water-resisting agent 123a and SiO 2 Thin film layer 122 is that medium carries out Chemical bond with airborne moisture, forms fluorine class waterproof layer 123.
Shown in Figure 31 E is the figure that attaches the operation of self adhesive tape 124.On the coated face of fluorine class waterproof layer 123, stick self adhesive tape 24.When attaching this self adhesive tape 124, make it not produce bubble.This is because if bubble is arranged, the nozzle bore then offered in the residing position of bubble can make quality variation because adding the dirt settling etc. in man-hour.
Shown in Figure 31 F is the figure of the manufacturing procedure of nozzle bore 44.In this operation,, form nozzle bore 44 from polyimide film 121 1 sides irradiation excimer laser.After the processing of nozzle bore 44, use release adhesive band 124 backs.In addition, omitted the explanation of the high rigid element 125 that uses for the rigidity that improves the illustrated nozzle plate of Figure 29 43 here, if but in this operation, use, then preferably between Figure 31 D operation and Figure 31 E operation, implement.
Figure 32 is the figure that the summary of the device that uses when making ink gun by ink gun manufacture method of the present invention is shown.
This device is the device by the square law deviceization that will be called as " メ モ one De プ ロ セ ス " of the OCLI of the U.S. (OPTICAL COATING LABORATORY INC.) exploitation, is used for the making of antireflection film such as indicating meter or antifouling film.Shown in figure 32,4 positional alignment Si sputter devices 202, O around drum 210 2Ion gun 203, Nb sputter device 204, オ プ Star one Le evaporator 205, its integral body be arranged in can vacuum take-off the chamber.At first, adopt Si sputter device 202 that Si is carried out sputter, pass through O then 2Ion gun 203 makes O 2Ion contacts with Si and becomes SiO 2Then, by Nb sputter device 204, オ プ Star one Le evaporator 205 suitable evaporation Nb, オ プ Star one Le DSX.Under the situation of antireflection film, with the regulation thickness with Nb and SiO 2Carry out evaporation after the number of plies of superimposed necessity.Under the situation of the present invention,, therefore Nb can not needed and only additional SiO owing to do not need the function of antireflection film 2, オ プ Star one each one deck of Le DSX.By using this device, as mentioned above, SiO can formed 2Behind the thin layer 122, directly in vacuum chamber, implement the vacuum evaporation of オ プ Star one Le DSX.
The critical surface tension of above-mentioned anti-ink lay is preferably 5～40mN/m, more preferably 5～30mN/m.If above-mentioned critical surface tension surpasses 30mN/m, when life-time service, can produce nozzle plate by the excessive wetting phenomenon of printing ink, when printing repeatedly, the discharge bending or the particlized that produce printing ink sometimes are unusual, if surpass 40mN/m, then owing to just produce printing ink to the excessive wetting phenomenon of nozzle plate from the initial stage, it is unusual therefore just to produce the discharge bending or the particlized of printing ink from the initial stage sometimes.
In fact, be coated on the aluminium base and carry out heat drying and make the nozzle plate that has anti-ink lay by showing the anti-printing ink material shown in the B.The critical surface tension of the anti-ink lay of measuring is as shown in table 2.
Here, above-mentioned critical surface tension can be obtained by the Zisman method.That is, the known fluid drips of surface tension on anti-ink lay, is measured contact angle θ, be the x axle, be y axle when drawing with the surface tension of liquid, the straight line that is tilted to the right (Zisman Plot) with cos θ.Surface tension in the time of can calculating this straight line Y=1 (θ=0) is as critical surface tension γ c.As other method, can use Fowkes method, Owens and Wendt method, Van Oss method to obtain critical surface tension.
In addition, with above-mentioned ink gun making method similarly, use the nozzle plate have anti-ink lay to make ink gun.Use following cyan ink (cyan ink of Production Example 1 described later) to its ink jet.The process of circling in the air of video recording photography printing ink is also observed, and can confirm particlized normally when using arbitrarily nozzle plate, and it is also good to discharge stability.The results are shown in table B.
＜cyan ink 〉
Add 20.0 quality % and contain the microparticle dispersion of copper phthalocyanine, 23.0 the 3-methyl isophthalic acid of quality %, the 3-butyleneglycol, 8.0 quality % glycerine, 2.0 the 2-methyl isophthalic acid of quality %, the 3-hexylene glycol, 2.5 the FS-300 of quality % (manufacturing of Dupont company) as fluorine class tensio-active agent, 0.2 the プ ロ キ セ Le LV of quality % (manufacturing of ア ベ シ ア company) as Antisepticize and mildew preventive, 0.5 quality %2-amino-2-ethyl-1, ammediol, and an amount of ion exchanged water, making total amount is 100 quality %, then, the membrane filter with mean pore size 0.8 μ m filters.Thus, preparation cyan ink.
[table B]
Trade(brand)name Critical surface tension Discharge stability
East レ ダ ウ コ one ニ Application グ (strain) SR2411 21.6mN/m Well
SHIN-ETSU HANTOTAI's chemical industry (strain) KBM7803 16.9mN/m Well
SHIN-ETSU HANTOTAI's chemical industry (strain) KP801M 6.6mN/m Well
Here, with reference to accompanying drawing an embodiment that adopts ink-jet recording device of the present invention to implement ink jet recording method of the present invention is described.Fig. 3 is the sketch chart that an example of ink-jet recording device of the present invention is shown.This ink-jet recording device shown in Figure 3 has apparatus main body 1, be installed in being used in this apparatus main body 1 load paper paper feed tray 2, be installed in apparatus main body 1 and be used for discharge tray 3, the print cartridge filling department 6 of the paper of stored record (formation) image.Operating portions 7 such as setting operation key or indicating meter on print cartridge filling department 6.Print cartridge filling department 6 have be used to load and unload print cartridge 10 can switch protecgulum 8.
As shown in Figure 4 and Figure 5, in apparatus main body 1, utilization omitted illustrated crossbearer on the left side plate as the guide rod 11 of guiding parts and stay (stay) 12 with carriage (carriage) 13 free slidings remain on the main scanning direction, and by main scan motor (not shown), direction is carried out motion scan shown in the arrow in Fig. 5.
On carriage 13, ink droplet is discharged direction install down by discharging the record-header 14 that yellow (Y), cyan (C), pinkish red (M), the versicolor record of black (Bk) 4 ink-vapor recordings with ink droplet constitute with record-header, and make a plurality of printing ink relief outlets along the direction arrangement that intersects with main scanning direction.
As the ink-vapor recording record-header that constitutes record-header 14, can use the piezoelectric driving systen that possesses piezoelectric element etc., use electrothermal conversioning element such as heating resistor, utilize the phase transformation that the film boiling of liquid causes thermal actuator, utilize the metal phase change that temperature variation causes shape memory alloy actuator, to utilize the conducts such as electrostatic actuator of electrostatic force to be used to discharge the record of energy generating apparatus of recording ink first-class.
In addition, the pilot trench of all kinds 15 that is used for to record-header 14 each color ink of supply is installed on carriage 13.By not shown recording ink supply pipe, from filling in the print cartridge of the present invention 10 of print cartridge filling department 6, to pilot trench 15 supplies and additional above-mentioned recording ink of the present invention.
On the other hand, as the paper feed part that is used to supply the paper 22 in the paper loading portion (pressing plate) 21 that is loaded in paper feed tray 2, possess separately the first quarter moon roller bearing (paper feeding roller bearing 23) of paper 22 and relative with this paper feeding roller bearing 23 separating pad of being made by the big material of frictional coefficient 24 one by one from paper loading portion 21, this separating pad 24 is close proximity to paper feeding roller bearing 23 1 sides.
As the delivery section that the paper 22 that provides by this paper feed part is provided below record-header 14, the travelling belt 31 that possesses electrostatic adhesion paper 22 and carry, be clipped between the travelling belt 31, the reverse rollers 32 of the paper 22 that conveying is carried by liner 25 from paper feed part, make 90 ° of directions of paper 22 conversion directly over being transported to roughly arrive transmission liner 33 on the travelling belt 31, utilize push part 34 to be close proximity to the front end pressurization roller bearing 35 of travelling belt 31 sides, in addition, also possesses the charged roller 36 that is used to make travelling belt 31 surface chargings as Charging system.
Travelling belt 31 is endless belts, is drawn to be located between transfer roller 37 and the tensioning roller 38, and can detour on the band delivery direction.On the back side of travelling belt 31, guiding parts 77 correspondingly is set with the zone that utilizes record-header 14 to print.In addition,, possess the disengaging pawl 51, exit roller 52 and the row's paper roller bearing 53 that separate paper 22 from travelling belt 31, discharge tray 3 is set below exit roller 52 as the row's paper portion that is used to discharge the paper 22 that utilizes record-header 14 records.
Two sides paper feeding element 61 releasably is installed on the back side of apparatus main body 1.Two sides paper feeding element 61 receives the paper 22 that returns by the opposite spin of travelling belt 31, and makes it upset, provides once more between reverse rollers 32 and the travelling belt 31.In addition, on two sides paper feeding element 61, manual feed portion 62 is set.
This ink-jet recording device separates paper 22 one by one from paper feed part and carries out paper feeding, and paper feeding to the paper 22 roughly is directed to device 25 guiding, is held between travelling belt 31 and the reverse rollers 32 and transmits.In addition, utilize and transmit liner 33 guiding tops, and utilize top pressurization roller bearing 35 to be urged to travelling belt 31, and change roughly 90 ° delivery direction.
At this moment, make travelling belt 31 charged by charged roller 36, paper 22 is transmitted in travelling belt 31 by electrostatic adhesion.So, Yi Bian by carriage 13 is moved, Yi Bian according to picture signal activation record head 14, spray ink droplet to the paper 22 that stops, record delegation behind the paper 22 of transmission specified amount, carries out the record of next line.The signal by accepting record end or the rear end of paper 22 arrive the signal of posting field, and the end record operation is expelled to discharge tray 3 with paper 22.
And, tail off in case detect the residual quantity of the recording ink in the pilot trench 15, just the recording ink of aequum is supplemented to pilot trench 15 from print cartridge 10.
Also have, the example by tandem type (shuttle type) ink-jet recording device that carriage is applied to scan is illustrated here, but is applicable to the line-type ink-jet recording device that possesses the line style record-header too.
Here, record-header 14 (use be the general name of a plurality of record-headers) is for example shown in Figure 6, the liquid droplet ejecting head 14a by the nozzle rows 14mn that has the nozzle rows 14yn that is made up of a plurality of nozzle N that spray yellow (Y) ink droplet and is made up of a plurality of nozzle N that spray pinkish red (M) ink droplet, the splash head 14b formation that has nozzle rows 14cn that a plurality of nozzle N by the ink droplet that sprays cyan (C) form and deceived the nozzle rows 14kn that a plurality of nozzle rows of (Bk) ink droplet form by injection.
In addition, this situation is to provide 2 kinds of colors by 2 different pilot trench to a record-header, and utilize 2 record-headers of 4 pilot trench to carry out the figure in 4 looks when printing of Y, M, C and black, 4 record-headers with 2 row nozzle rows can also be set, prepare the pilot trench of each 1 different colours respectively, thereby by 4 record-headers with 2 row nozzle rows, 4 pilot trench printings Y, M, C and four kinds of colors of black.
The example of this Fig. 6 is represented ink-jet printer (company of Ricoh makes, IPSiO G505), and the nozzle that sprays the printing ink of different colours to identical record-header is set side by side.
In addition,, omitted diagram, but be provided with the record-header of 4 same structures, yellow, magenta, cyan and black ink are provided respectively for ink-jet printer (company of Ricoh makes, IPSiO G707).
Box, pilot trench and the record-header of supply moisture retention liquid further are set near record-header, when stopping using for a long time, spray moisture retention liquid to the cladding system (lid of preserving moisture) that covers this record-header nozzle position, thereby can prevent the drying at nozzle position.When spraying in the lid of preserving moisture like this, as solid substances few (perhaps not having fully) such as the preferred tinting materials of moisture retention liquid, water is the liquid of main body.
In addition, in ink-jet printer (company of Ricoh makes, IPSiO G505), identical record-header has 2 pilot trench, nozzle rows, can also be pilot trench, the nozzle rows of a side as moisture retention liquid.At this moment, the record-header that is provided with the pilot trench of the pilot trench of moisture retention liquid and coloring printing ink is set to 4 of cyan, magenta, yellow and black.
At this moment, have moisture retention liquid and recording ink in the same record-header, therefore, moisture retention liquid also plays the effect of the washings of painted recording ink when record-header cleans.
Between the pilot trench of this moisture retention liquid and coloring printing ink, perhaps between the passage at pilot trench arrival nozzle position, valve system is set all, can be formed on and open this valve when stopping using for a long time, to the nozzle position of this coloring printing ink supply moisture retention liquid, and be replaced as the mechanism of the nozzle position exsiccant moisture retention liquid that is difficult for making coloring printing ink.
Even the mechanism that keeps that utilizes such moisture retention liquid is not set, also can carry out applying the not sky scanning of the forceful electric power pressure of ink jet to piezoelectric element, thereby prevent the fixed of nozzle position, perhaps can spray acceptor site (ink collection position) ink jet by the sky beyond recording medium, carry out the empty injection of what is called continually, thereby prevent spray nozzle clogging.Preferably must carry out sky at least between 1 page of printing sprays.
As the ink gun that constitutes record-header 14, can utilize the piezoelectric driving systen that possesses piezoelectric element etc., heating resistor etc. to use electrothermal conversioning element, utilize the phase transformation that the film boiling by liquid causes thermal actuator, utilize the metal phase change that causes by temperature variation shape memory alloy actuator, utilize the conducts such as electrostatic actuator of electrostatic force to be used for the ink gun of the energy producing unit of ink jet.In addition, in the embodiment of back, the ink gun that piezoelectric driving systen (piezoelectric element) is used for energy producing unit has been installed.
In addition, at the pilot trench 15 that each nozzle rows 14yn, 14mn of being used for respectively to record-header 14, conduct fluid container of all kinds that 14cn, 14kn supply each color ink have been installed on the carriage 13 (when difference is of all kinds, corresponding with nozzle rows, use symbol 15y, 15m, 15c, 15k).By ink supply tube 16, replenish printing ink to this pilot trench 15 from above-mentioned major trough of all kinds (print cartridge) 10 (when difference when of all kinds, corresponding, use symbol 10y, 10m, 10c, 10k) with nozzle rows.Wherein, major trough 10 respectively with each color ink that holds yellow (Y), cyan (C), pinkish red (M), black (Bk) accordingly of all kinds, but holding the volumetric ratio of holding of printing ink of major trough 10k of black ink, to hold major trough 10y, 10m, the 10c of other color inks bigger.
Below, describe ink supply unit in detail with reference to Fig. 7～Fig. 9 as the liquid supplying apparatus in this recording unit.Fig. 7 is the exploded perspective view of relevant portion in the identical ink supply unit, and Fig. 8 is its detail drawing, and Fig. 9 is the side-view of the pattern of same pilot trench.
This ink supply unit is installed on the carriage 13 and constituting to the replenish the supply major trough (print cartridge) 10 of printing ink of this pilot trench 15 as the pilot trench 15 of fluid container with by supply pipe 16 to each record-header 14 (14a, 14b) supply printing ink by aforesaid.
In 1 pilot trench 15, hold in formation by bonding or fusion etc. to attach on the container body (housing main body) 101 of printing ink accommodation section 100 of printing ink opening (one side of the pilot trench 15) sealing of printing ink accommodation section 100 had a flexible film-like members (the membranaceous parts of flexible thin) 102, in addition, be provided with in 100 inside, printing ink accommodation section and be used to make film-like members 102 spring (spring) 103 near the elastomeric element of outside between housing main body 101 and film-like members 102.
Wherein, above-mentioned film-like members 102 can be a single layer structure, shown in Figure 10 A, can also be that diverse the 1st layer of 102a and the 2nd layer of 102b carry out lamination and the two-layer structure that obtains, for example, the structure of polyethylene and nylon film shape material being carried out lamination and obtaining perhaps shown in Figure 10 B, is formed in the 1st layer of 102a and goes up the structure that forms silica steam plating layer 102c.By making such structure, can obtain anti-fluidity really to printing ink.In addition, contain the silica steam plating layer, also can seek to improve anti-fluidity for the printing ink that holds by making film-like members 102.
In addition, the thickness of film-like members 102 is preferably 10～100 μ m.If above-mentioned thickness is lower than 10 μ m, be easy to generate the breakage that causes by long-term deterioration etc. sometimes, if surpass 100 μ m, flexible reduction is difficult to produce effectively negative pressure sometimes.
In addition, on film-like members 102, form accordingly as the ridge 102a that protrudes shape with spring 103, and at its outside reinforcing member 104 that attaches.Like this, protrude the position, can stably keep elastomeric element (spring) 103 by on the membranaceous parts 102 of flexible thin, being provided with.At this moment, by flaky thin film component is made the protrusion shape, the membranaceous parts 102 of flexible thin can easily form and protrude the position.
In addition, on housing 101, be provided for replenishing the printing ink lead-in path portion 111 of printing ink, and the coupling device 112 that this printing ink of connection is led lead-in path portion 111 and the supply pipe 16 that links to each other with print cartridge 10 can freely be installed with dismantling to printing ink accommodation section 100.Between print cartridge 10 and pilot trench 15, be provided with from print cartridge 10 to the described infusion pump in the back of pilot trench 15 force feed printing ink.
In addition, below housing 101, install from printing ink accommodation section 100, on this interconnecting piece 113, form the printing ink feed path 114 of record-header 14 to the interconnecting piece 113 of record-header 14 supply printing ink, and printing ink accommodation section 100 between strainer 115 is installed.
And, be formed for from the air flow circuit 121 of printing ink accommodation section 100 release air on the top of housing 101.This air flow circuit 121 comprises the inlet circuit portion 122 and the circuit portion that with this inlet circuit portion 122 link to each other (be called " quadrature circuit portion ") 123 of opening towards printing ink accommodation section 100, be communicated with air open bore 131 on being arranged at housing 101 in the downstream, in addition, under user mode, be positioned at the partial continuous ground of air open bore 131 below more and form savings portion 126.
On this atmosphere opening hole 131, be provided for switching the air relief valve mechanism 132 of the air open system of air-tight state in the pilot trench 15 and air open state.This air relief valve mechanism 132 accommodates valve seat 134 in support (holder) 133, as the ball 135 of valve body with this ball 135 is close proximity to the spring 136 of valve seat 134 1 sides.
In addition, the effect of savings portion 126 is described, when apparatus main body tilted or waves, the possibilities in the printing ink invading air stream 121 improved.Therefore, the printing ink of invading from air flow circuit 121 can be put aside in savings portion 126, even have during conveying and fall to wait and produce printing ink and invade, also can prevent from because of printing ink invading air opening port 131 and make to solidify in the air relief valve mechanism 132 of its folding etc. to make air relief valve mechanism 132 malfunctions.
2 detecting electrodes 141,142 that the quantity of ink that is used to detect in the pilot trench 15 reaches (this state is called " no printing ink ") below the specified amount are installed above housing 101.Detecting electrode 141,142 all is immersed in state in the printing ink and state that at least one is not immersed in the printing ink changes the conducting state between the detecting electrode 141,142 by being in two, thereby can detect " no printing ink ".
Ink-jet recording device of the present invention such as Figure 11 and shown in Figure 12, in the non-printing zone of the side (perhaps also can be both sides) of the scanning direction of carriage 13, be provided for keeping, come and go record-header 14 nozzle state keep traverse mechanism (following also be called " subsystem ") 71.Figure 11 is a vertical view of keeping traverse mechanism, and Figure 12 is the diagrammatic illustration figure that keeps element.On this subsystem 71, possess cover 72A, the 72B of each nozzle face that is used to cover record- header 14a, 14b and be used for the scraper plate 73 of wiping nozzle face.Sky when between this cover 72A and scraper plate 73 the sky ink jet being set sprays susceptor.The formation that this sky sprays susceptor is: make ink jet extremely wherein, and flow in the waste liquid tank of below, this part (part of injection) adheres to printing ink easily, therefore, the scraper plate that automatically scrapes adherent printing ink is set.
Below, the traverse mechanism 71 of keeping that ink-jet recording device of the present invention is related to describes.
As Figure 11 and shown in Figure 12, if motor 231 is rotated in the forward, then rotate to motor gear 232, pump gear 234, neutral gear 235, neutral gear 236, neutral gear 237,220 work of pipe pump are aspirated in the lid to pump and pipe 219 rightmosts that are connected (posting field one side).Other gears are not connected with in the same way clutch coupling 237 and do not work.
If motor 231 reverse rotations, clutch coupling 237 in the same way connects, and rotates to the motor camshaft.220 reverse rotations of pipe pump, pump becomes idle structure.
(carriage lock cam) 227 of installation bracket locking cam on camshaft 221 and cap cam (capcam) 222B and 222A and scrape plane cam (wiper cam) 224 and wiped clean cam (wipercleaner cam) 228 and home sensor with cam 241, and it can whole be rotated.
Carriage lock 215 is close proximity to top (locking direction) by compression spring (not diagram).By the carriage lock arm 217 that the cam surface with carriage lock cam 227 contacts, carriage lock 215 is moved up and down.
Lid 72A and 72B, lid support 212A move up and down by lid cam 222A and 222B.
Scraper plate 73 moves up and down by scraping plane cam 228.
Scraper plate clearer 218 is close proximity to the direction that departs from scraper plate 73 by spring, and carries out work by scraper plate clearer cam 218 on the scraper plate direction.By scraper plate clearer 218 and the clamping of empty injection susceptor, one side descends scraper plate 73 on one side, thereby makes the printing ink of scraper plate 73 be dropped down onto the empty inside of spraying by wiping.
Keep and be fixed with transmitter (optical chopper/not shown) on the unit main body, its structure makes lid make HP control lever (not shown) work when reaching bottom by the original position cam, transmitter becomes open mode, the original position (home position) that detects motor (beyond the pump) (in addition, the HP control lever is not worked, and transmitter is normally closed).
During power source ON, it moves up and down (up to moving beginning, not carrying out position detection) in the mode with the location independent of lid 72A and 72B, lid support 212A and 212B, detect the original position (in the uphill process) of lid after, move the amount of determining and arrive bottom.Then, the carriage move left and right turns back to the position of lid behind the detection position, carries out the capping operation.
Job order during the motor counter-rotating is to carry out following a series of actions repeatedly: cover liter (carriage lock also almost rises simultaneously), lid decline (carriage lock also almost descends simultaneously), home position sensing is opened, scraper plate rises, scraper plate clearer start working (scraper plate is pressed into empty the injection on the susceptor), scraper plate descends (making scraper plate work with the scraper plate clearer), turns back to scraper plate clearer home position.
In ink-jet recording device of the present invention and ink jet recording method the various records applicable to the employing ink-jet recording, for example, particularly suitable ink-vapor recording printer, picture unit, copy device, printing/fax/duplicating equipment complex etc.
(ink medium group)
In the 1st embodiment, ink medium group of the present invention has recording ink and recording medium, also can contain other member in case of necessity, described recording ink comprises at least and contains tinting material and resin and be that solid solids component, boiling point are higher and be the liquid component and the water of liquid under 25 ℃ than water under 25 ℃, and the total content of this liquid component in above-mentioned recording ink is below the 20 quality %.
In addition, the content outside the recording ink in the ink medium group of above-mentioned the 1st embodiment above-mentioned is identical with above-mentioned recording ink of the present invention.
In the 2nd embodiment, ink medium group of the present invention has recording ink and by recording medium, also can contain other member in case of necessity.
In the 3rd embodiment, the recording medium that ink medium group of the present invention has recording ink and is made of non-porous base material also can contain other member in case of necessity.
As the recording ink in each the ink medium group in above-mentioned the 2nd embodiment and the 3rd embodiment, it comprises at least and contains tinting material and resin and be that solid solids component, boiling point are higher and be the liquid component and the water of liquid under 25 ℃ than water under 25 ℃;
The total content of aforesaid liquid composition in above-mentioned recording ink is below the 30 quality %;
In addition, for the recording ink in each the ink medium group in above-mentioned the 2nd embodiment and the 3rd embodiment, the content outside the total content of aforesaid liquid composition is identical with above-mentioned recording ink of the present invention.
In the 4th embodiment, ink medium group of the present invention comprises recording ink and recording medium;
Above-mentioned recording ink contains the colorant that contains water-insoluble or slightly water-soluble in polymer particles and pigment, water-dispersed resin particulate and the wetting agent of the polymer emulsion type that forms at least, the total solid amount of the pigment of above-mentioned polymer emulsion type and above-mentioned water-dispersed resin particulate is more than the 20 quality %, and the content of above-mentioned wetting agent is more than the 20 quality %.
In the 5th embodiment, ink medium group of the present invention comprises recording ink and recording medium;
Above-mentioned recording ink contains tinting material, water-dispersed resin particulate and wetting agent at least, the total content of the solid substance in this recording ink is more than the 20 quality %, the content of above-mentioned wetting agent is more than the 20 quality %, this wetting agent is independent glycerine, and perhaps the content of glycerine in above-mentioned wetting agent is more than the 80 quality %.
Such increase under the situation of recording ink of humectant content, in order to improve rate of drying, the forced drying operation is set preferably.As drying means, can be the method that drying installation is set before record, also can be in the method for drying installation any is set behind record.
As drying installation, can be to use microwave energy to give the device of microwave energy to paper, also can be the so contactless device of heater strip mode.The device (for example warming mill) of contact can also be set in addition, in addition.Directly pair roller heating itself, perhaps also can by other thermals source indirectly pair roller heat.
Recording medium as in the ink medium group of any mode in above-mentioned the 1st embodiment, the 2nd embodiment, the 4th embodiment and the 5th embodiment can use following medium.
＜recording medium 〉
Above-mentioned recording medium has support and the coating layer that is on face of this support, has other layer in addition as required.
In above-mentioned recording medium, duration of contact pure water during 100ms fixed with dynamic scan imbibition instrumentation is 2～35ml/m to the transfer amount of above-mentioned recording medium 2, be preferably 2～10ml/m 2
If the transfer amount of above-mentioned printing ink and pure water is very few under the duration of contact 100ms, then easily bubble sometimes, if too much, then record back dot diameter is more much smaller than desirable diameter sometimes.
Duration of contact pure water during 400ms fixed with dynamic scan imbibition instrumentation is 3～40ml/m to the transfer amount of above-mentioned recording medium 2, be preferably 3～10ml/m 2
If the transfer amount under the above-mentioned duration of contact 400ms is very few, then drying property is insufficient, therefore easily produces sometimes and quickens trace, if too much, the gloss of then dry sometimes back image section is easy to step-down.
Here, above-mentioned dynamic scan imbibition meter (dynamic scanning absorptometer, DSA, paper パ skill Association Chi, the 48th volume, in May, 1994, the 88th～92 page, the idle weight then) is the device that can correctly measure liquid absorption in the extremely short time.Above-mentioned dynamic scan imbibition meter is a kind of automatic assay device, measure in the following manner, promptly directly read rate of liquid aspiration from moving of meniscus capillaceous, it is discoid that sample is become, thereon with spirrillum scanning imbibition head, automatically change sweep velocity by predefined pattern, 1 sample is only measured necessity count.Supply head to paper sample supply liquid passes through teflon (registered trademark) pipe coupling on kapillary, automatically directly reads the position of meniscus in the kapillary with optical pickocff.Specifically, be to use dynamic scan imbibition meter (K350 series D type, consonance Jinggong Co., Ltd makes) to measure the amount of movement of pure water or printing ink.Transfer amount under duration of contact 100ms and the duration of contact 400ms can by interpolation technique from duration of contact of each of neighbour duration of contact under the measured value of transfer amount obtain.
-support-
As above-mentioned support, there is no particular limitation, can suitably select according to purpose, for example can enumerate paper based on lumber fibre, based on such flaky substance of the non-woven of lumber fibre and synthon etc.
As above-mentioned paper, be not particularly limited, can from known paper, suitably select according to purpose, for example can use for example wood pulps, old paper pulp etc.As above-mentioned wood pulps, for example can enumerate bleaching wealthy wooden kraft pulp (LBKP), bleaching pin wood kraft pulp (NBKP), NBSP, LBSP, GP, TMP etc.
As the raw material of above-mentioned old paper pulp, can enumerate shown in the ancient paper standard quality specification table at the ancient paper regeneration promotion of consortium as a juridical person center go up white, Squares-of-a-chessboard white (white with rule mark), milky white, card, extra white, in white, simile(printing)paper, look white (color white), plotting paper, in vain cut on enamelled paper, the spy (special high cut), cut (another high cut), newspaper, magazine etc. on not.Specifically, can enumerate as printer medias such as the relevant non-coating accounting machine paper of information, temperature-sensitive paper, impact papers with paper; PPC is with the old paper of OA such as paper; Coated paper such as enamelled paper, White Board, little White Board, matt paper; Vellum, colored vellum (color higt quality paper), note, notepaper, wrapping paper, fax with paper, medium paper, newspaper with paper, contain paper such as uncoated paper such as ground wood pulp system paper, overweight paper, simile(printing)paper, pure white coil paper, milk carton board, or contain pulp based paper etc. as chemical pulp paper, the high rate of finished products of the old paper of paperboard.These paper can use a kind separately, also can use simultaneously more than 2 kinds.
Above-mentioned old paper paper pulp is the combination manufacturing of following four operations of process usually.
(1) dissociates, use hollander, old paper is handled, disassemble into fibrously, peel off printing-ink from fiber by mechanical force or chemical reagent;
(2) foreign matter (plastics etc.) and the rubbish that contains in the old paper is removed in dedusting with screen cloth, eradicator etc.;
(3) deinking, the printing-ink that will use tensio-active agent to peel off from fiber by flotation process or washing out method is scavenged into outside the system;
(4) bleaching utilizes oxygenizement or reductive action to improve the whiteness of fiber.
Under the situation of mixing above-mentioned old paper paper pulp, consider that from preventing wrinkling aspect, record back the mixture ratio of old paper paper pulp is below 40% in preferred all paper pulp.
In using in the above-mentioned support, add filler, for example can use present known pigment as white pigment.As above-mentioned white pigment, for example can enumerate white inorganic pigments such as light calcium carbonate, water-ground limestone, kaolin, clay, talcum, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulphide, zinc carbonate, stain white, pure aluminium silicate, diatomite, Calucium Silicate powder, Magnesium Silicate q-agent, synthetic silica, aluminium hydroxide, aluminum oxide, lithopone, zeolite, magnesiumcarbonate, magnesium hydroxide; Pigment dyestuffs such as styrene plastic pigment, acrylics pigment, polyethylene, microcapsule, urea resin, melamine resin etc.These materials can use a kind separately, also can use simultaneously more than 2 kinds.
Add sizing agent in using when manufacturing paper with pulp above-mentioned support, for example can enumerate and be used for neutrality and copy the neutral rosin based sizing agent of paper, alkenyl succinic anhydrides (ASA), alkyl ketene dimer (AKD), tree oil lipid sizing agent etc.Wherein, neutral rosin based sizing agent or alkenyl succinic anhydrides are suitable especially.Therefore the sizing action of abovementioned alkyl ketene dimer is strong, adds get final product on a small quantity, but easily the make paper used for recording skin friction coefficient decline of (medium), so the conveying aspect during from ink-vapor recording is worthless sometimes.
-coating layer-
Above-mentioned coating layer contains pigment and tackiness agent (binding agent), also can contain tensio-active agent and other composition in case of necessity.
As pigment, can use mineral dye, or use mineral dye and pigment dyestuff simultaneously.
As above-mentioned mineral dye, for example can enumerate kaolin, talcum, water-ground limestone, light calcium carbonate, calcium sulfite, amorphous silica, titanium dioxide, magnesiumcarbonate, titanium dioxide, aluminium hydroxide, calcium hydroxide, magnesium hydroxide, zinc hydroxide, chlorite etc.Wherein, kaolinic presenting property of gloss excellence can form the feel that approaches offset paper, is particularly preferred thus.
In above-mentioned kaolin, delaminated kaolins, sintering kaolin arranged, carried out engineering kaolin of surface modification etc. etc., if consider presenting property of gloss, the kaolin that then preferably has the following particle ratio of particle diameter 2 μ m and be the above size distribution of 80 quality % accounts for all more than the kaolinic 50 quality %.
Preferred above-mentioned kaolinic addition is more than 50 mass parts with respect to above-mentioned binding agent 100 mass parts.If above-mentioned addition less than 50 mass parts then may can not get enough effects aspect glossiness.There is no particular limitation for the upper limit of above-mentioned addition, if but consider kaolinic flowability, particularly tackifying under high shear, then, preferably be less than 90 mass parts from coating adaptability aspect.
As above-mentioned pigment dyestuff, the water-soluble dispersion of styrene-propene acid copolymer particle, styrene-butadiene copolymer particle, polystyrene particle, polyethylene particles etc. is for example arranged.These pigment dyestuffs can also mix more than 2 kinds.
The addition of preferred above-mentioned pigment dyestuff is 2～20 mass parts with respect to whole pigment 100 mass parts of above-mentioned coating layer.Presenting property of the gloss excellence of above-mentioned pigment dyestuff, its proportion are littler than mineral dye, can obtain therefore that volume is big, high gloss, the good coating layer of surface-coated property.If above-mentioned addition less than 2 mass parts then do not have above-mentioned effect, if surpass 20 mass parts, then the mobile variation of coating fluid causes being coated with operability and descends, and also is uneconomic from cost.
As above-mentioned pigment dyestuff, its form has compact-type, hollow type, annular etc., but in view of the equilibrium of presenting property of gloss, surface coverage and coating fluid flowability, preferably adopting median size is 0.2～3.0 μ m, and more preferably voidage is the hollow type more than 40%.
As above-mentioned binding agent, preferably use water-base resin.
As above-mentioned water-base resin, preferably use at least a in water soluble resin and the water-dispersed resin.As above-mentioned water soluble resin, there is no particular limitation, can suitably select according to purpose, for example can enumerate the modifier of polyvinyl alcohol such as polyvinyl alcohol, anion-modified polyvinyl alcohol, cation-modified polyvinyl alcohol, ethylidene ether modification polyvinyl alcohol; The modifier of the Polyvinylpyrolidone (PVP)s such as multipolymer of the multipolymer of the multipolymer of the multipolymer of urethane, Polyvinylpyrolidone (PVP) and polyvinylpyrrolidone and vinyl acetate, vinyl pyrrolidone and dimethylaminoethyl methacrylate, class vinyl pyrrolidone and dimethylaminoethyl methacrylate, vinyl pyrrolidone and Methacrylamide propyl group chlorination trimethyl ammonium; Mierocrystalline celluloses such as carboxymethyl cellulose, Natvosol, hydroxypropylcellulose; Cellulosic modifiers such as cationization Natvosol; The synthetic resins such as multipolymer of polyester, polyacrylic acid (ester), melamine resin or their modifier, polyester and urethane; Poly-(methyl) vinylformic acid, poly-(methyl) acrylamide, Sumstar 190, organic phosphate starch, from structural reform starch, cationic starch or various treated starch, polyethylene oxide, sodium polyacrylate, sodiun alginate etc.These materials can use a kind separately, also can use simultaneously more than 2 kinds.
Wherein, from the viewpoint of absorbency, the multipolymer of special preferably polyethylene alcohol, cation-modified polyvinyl alcohol, ethylidene ether modification polyvinyl alcohol, polyester, urethane, polyester and urethane etc.
As above-mentioned water-dispersed resin, be not particularly limited, can suitably select according to purpose, for example can enumerate polyvinyl acetate (PVA), ethylene-vinyl acetate copolymer, polystyrene, vinylbenzene-(methyl) acrylate copolymer, (methyl) acrylic polymer, vinyl acetate-(methyl) vinylformic acid (ester) multipolymer, styrene-butadiene copolymer, ethylene-propylene copolymer, polyvingl ether, organosilicon-acrylic copolymer etc.In addition, can contain linking agents such as methylolation trimeric cyanamide, methylolation urea, methylolation hydroxyl propylene urea, isocyanic ester, also can be have a self-crosslinking contain unitary multipolymers such as N hydroxymethyl acrylamide.Also can use multiple these water-base resins simultaneously.
The addition of preferred above-mentioned water-base resin is 2～100 mass parts with respect to above-mentioned pigment 100 mass parts, more preferably 3～50 mass parts.The definite of the addition of above-mentioned water-base resin will make the imbibition characteristic of recording medium be in the scope of expection.
Using under the situation of water dispersible tinting material as above-mentioned tinting material, not necessarily will add the cationic organic compound, but there is no particular limitation, can suitably select according to purpose.For example, can enumerate the monomer, oligopolymer, polymkeric substance etc. that can react primary～tertiary amine of generating insoluble salt, quaternary ammonium salt, wherein preferred oligopolymer or polymkeric substance with substantive dyestuff in the water-based ink or the sulfonic group in the matching stain, carboxyl, amino etc.
As above-mentioned cationic organic compound, can enumerate dimethylamine/Epicholorohydrin polycondensate, dimethylamine/ammonia/Epicholorohydrin condenses, poly-(methacrylic acid trimethylammonium ammonia ethyl ester/Methylsulfate), diallyl amine hydrochlorate/acrylamide copolymer, poly-(diallyl amine hydrochlorate/sulfurous gas), the PAH hydrochloride, poly-(allylamine hydrochloride/diallyl amine hydrochlorate), acrylamide/diallyl amine multipolymer, the polyvinylamine multipolymer, the dicyano diamide, dicyano diamide/ammonium chloride/urea/formaldehyde condensation products, polyalkylene polyamine/dicyano diamide ammonium salt condenses, dimethyl diallyl ammonium chloride, polysalt diene acid propyl group methylamine, poly-(diallyldimethylammonium chloride), poly-(diallyldimethylammonium chloride/sulfurous gas), poly-(diallyldimethylammonium chloride/hydrochloric acid diallylamine derivatives), acrylamide/diallyldimethylammonium chloride multipolymer, acrylate/acrylamide/hydrochloric acid diallyl amine multipolymer, poly-second is embraced imines, second such as acrylamide polymer are embraced imine derivative, poly-second is embraced imines epoxy alkane modifier etc.These materials can use a kind separately, also can use simultaneously more than 2 kinds.
Wherein, preferably combination is used the cationic organic compound of low-molecular-weight cationic organic compound such as dimethylamine/Epicholorohydrin polycondensate, polysalt acid allyl amine and other higher molecular weight, for example poly-(diallyldimethylammonium chloride) etc.By using them simultaneously, compare during with independent use and can improve image color, further alleviate the profit of spreading and sinking in.
The cation equivalent that the colloid titration method of above-mentioned cationic organic compound (using polyvinyl vitriolate of tartar, toluidine blue) is measured is preferably 3～8meq/g.If above-mentioned cation equivalent is in this scope, then the scope at above-mentioned dry pickup can obtain good result.
Here, when adopting above-mentioned colloid titration cation equivalent, with distilled water diluting cationic organic compound, making solid substance is 0.1 quality %, does not carry out pH regulator.
The dry pickup of preferred above-mentioned cationic organic compound is 0.3～2.0g/m 2If the dry pickup of above-mentioned cationic organic compound is lower than 0.3g/m 2, then can not be improved image color sometimes fully and be alleviated the effect of spreading and sinking in and moistening.
As above-mentioned tensio-active agent, there is no particular limitation, can suitably select according to purpose, can use the arbitrary substance in anion active agent, cationic active agent, amphoteric surfactant, the tween.Wherein, preferred especially tween.By adding above-mentioned tensio-active agent, improving the water-proof while of image, can also improve image color, improve the profit phenomenon of spreading and sinking in.
As above-mentioned tween, for example can enumerate the higher alcohols ethylene oxide adduct, the alkylphenol ethylene oxide adduct, the lipid acid ethylene oxide adduct, the polyhydric alcohol fatty acid ester ethylene oxide adduct, senior fatty amine ethylene oxide adduct, the fatty amide ethylene oxide adduct, greasy ethylene oxide adduct, the polypropylene glycol ethylene oxide adduct, the fatty acid ester of glycerine, the fatty acid ester of tetramethylolmethane, the fatty acid ester of Sorbitol Powder and sorbitan, the fatty acid ester of sucrose, the alkyl oxide of polyvalent alcohol, the fatty amide of alkanolamine etc.These materials can use a kind separately, also can use simultaneously more than 2 kinds.
As above-mentioned polyvalent alcohol, there is no particular limitation, can suitably select according to purpose, for example can enumerate glycerine, TriMethylolPropane(TMP), tetramethylolmethane, Sorbitol Powder, sucrose etc.In addition, for ethylene oxide adduct, can keep in the water miscible scope, it is effective replacing a part of oxyethane with propylene oxide or butylene oxide ring.Preferred replacement rate is below 50%.The HLB of above-mentioned tween (wetting ability/lipophilicity than) is preferably 4～15, and more preferably 7～13.
The addition of preferred above-mentioned tensio-active agent is 0～10 mass parts with respect to above-mentioned cationic organic compound 100 mass parts, more preferably 0.1～1.0 mass parts.
In above-mentioned coating layer, can in the scope of not damaging purpose of the present invention and effect, add other composition as required.As this other composition, can enumerate additives such as alumina powder, pH regulator agent, sanitas, oxidation inhibitor.
As the formation method of above-mentioned coating layer, there is no particular limitation, can suitably select according to purpose, can implement by the method for dipping on above-mentioned support or coating coating layer liquid.As the method for flooding or applying above-mentioned coating layer liquid, there is no particular limitation, can suitably select according to purpose, for example can adopt conventional spreadometer, door roll-type spreadometer, film to shift various coating machines such as spreadometer, scraper plate coating machine, rod coater, Kohler coater, curtain formula coating machine and be coated with, but consider from the cost aspect, also can shift spreadometer etc. and flood or adhere to, can also carry out precision work on the machine with being arranged on conventional spreadometer in the paper machine, door roll-type spreadometer, film.
The adhesion amount of above-mentioned coating layer liquid is not particularly limited, and can suitably select according to purpose, in solid substance, is preferably 0.5～20g/m 2, 1～15g/m more preferably 2
After carrying out above-mentioned dipping or coating, can carry out drying in case of necessity, there is no particular limitation for the drying temperature of this moment, can suitably select according to purpose, but be preferably about 100～250 ℃.
For above-mentioned recording medium, can between support and coating layer, and form other layer between support and the bottom further at the internal surface formation bottom of support, protective layer can also be set on coating layer.These layers can be individual layers, also can be multilayers.
As above-mentioned recording medium,, except ink jet recording medium, also can be commercially available offset printing White Board, intaglio printing with White Board etc. if the imbibition characteristic is in the scope of the present invention.
The Substance of above-mentioned recording medium is preferably 50～250g/m 2, 50～200g/m more preferably 2If above-mentioned Substance is less than 50g/m 2, the generation recording medium is blocked in the way of transport path easily owing to there is not stiffness waits conveying bad.On the other hand, if above-mentioned Substance surpasses 250g/m 2, then recording medium can not be crooked in the way of transport path because stiffness is excessive, still is easy to generate the blocked grade of recording medium and carries bad.
In addition, in the ink-jet media group that the 2nd embodiment of the present invention relates to, use non-porous base material as above-mentioned recording medium.
As above-mentioned non-porous base material, for example can enumerate plastic film, plastic layer platen, plastic coated paper, glass, metal etc.These materials are not have the recording medium of common aqueous inkjet recording with the water-retaining capacity that paper had.
As above-mentioned plastic film, for example can enumerate polyester (PET) film, polyolefin film etc.Here, PET film for example can be sneaked into about about 10% inorganic particles filler usually.
Above-mentioned plastic coated paper is to carry out coating with plastic material to handle or dip treating, and the resin treatment paper that paper facer coats with plastic material etc. has the film on plastics surface.
Be coated with water-absorbing material in common ink-jet on the OHP sheet material, but also can print on the non-water-absorbent sheet of such coating not carrying out among the present invention.
In addition, can also on as the glass of non-porous base material, metal, print.
(ink recorded matter)
Ink recorded matter by ink-jet recording device of the present invention and ink jet recording method record is an ink recorded matter of the present invention.Ink recorded matter of the present invention has the image that forms by recording ink on recording medium.
As above-mentioned recording ink, it comprises at least and contains tinting material and resin and be that solid solids component, boiling point are higher and be the liquid component and the water of liquid under 25 ℃ than water under 25 ℃;
The total content of aforesaid liquid composition in above-mentioned recording ink is below the 20 quality %;
The total content of above-mentioned solids component in above-mentioned recording ink is more than the 20 quality %, and the above-mentioned relatively solids component total amount of the total content of the resinous principle in this solids component is 40～95 quality %.
As above-mentioned recording medium, have no particular limits, can suitably select according to purpose, for example can enumerate common paper, coated paper for printing, glossy paper, special paper, cloth, film, OHP sheet etc.These media can use a kind separately, also can use simultaneously more than 2 kinds.Wherein, preferably use at least a in common paper and the coated paper for printing.
From cheap aspect, above-mentioned common paper is favourable.In addition, compare with glossy paper, above-mentioned coated paper for printing is relatively more cheap and can form level and smooth glossiness image, is favourable thus.But its drying property is poor, be difficult to usually be applied in the ink-jet purposes, but recording ink of the present invention can improve drying property, therefore can use.
Above-mentioned coated paper for printing is the recording medium that is made of support and at least one the lip-deep coating layer that is arranged at this support, is 2～35ml/m with pure water under dynamic scan imbibition instrumentation timing 100ms duration of contact to the transfer amount of recording medium 2, and pure water is 3～40ml/m to the transfer amount of recording medium under the duration of contact 400ms 2Compare with paper with commercially available ink-jet, these paper are transfer amount, i.e. the little material of water-retaining capacity.
For wherein transfer amount is few especially, i.e. the low recording medium of water-retaining capacity, recording ink of the present invention is effective especially.Specifically, with dynamic scan imbibition instrumentation fixed duration of contact under the 100ms pure water be 2～10ml/m to the transfer amount of recording medium 2, and pure water is 3～10ml/m to the transfer amount of recording medium under the duration of contact 400ms 2
When the liquid transfer amount under the above-mentioned duration of contact 100ms during less than above-mentioned scope, easily bubble, when being higher than above-mentioned scope, may make ink-jet diameter behind the record excessively less than the expection diameter.When the liquid transfer amount under the above-mentioned duration of contact 400ms during less than above-mentioned scope, drying property is insufficient, easily produces and quickens trace, and the gloss at dried image position is descended.But they finally relate to time of drying, for the recording ink of the present invention that has reduced the high boiling liquid composition, even for the paper less than above-mentioned scope, are improving the effect that also has on the drying property to a certain degree.
The paper that these water-retaining capacities are little can be used as commercially available acquisitions such as offset printing White Board.
In addition, recording medium is made of non-porous base material, and this non-porous base material is preferably selected from any materials in plastic film, plastic layer platen, plastic coated paper, glass and the metal.As above-mentioned plastic film, special preferred polyester film.
Above-mentioned ink recorded matter can form high image quality, does not ooze and spreads and sinks in, and the ageing stability excellence has been suitable for writing down the various uses such as data of various printing words and even image.
Embodiment
Below, embodiments of the invention are described, but the present invention never is confined to these embodiment.
(Production Example 1)
The preparation of-polymers soln A-
The 1L flask interior of having equipped mechanical stirrer, thermometer, nitrogen ingress pipe, return line and dropping funnel is fully replaced with nitrogen, mix 11.2g vinylbenzene, 2.8g vinylformic acid, 12.0g lauryl methacrylate(LMA), 4.0g polymethyl acrylic acid glycol ester, 4.0g vinylbenzene macromole and 0.4g mercaptoethanol then, be warmed up to 65 ℃.Then, through in flask, dripping the mixing solutions of 1 00.8g vinylbenzene, 25.2g vinylformic acid, 108.0g lauryl methacrylate(LMA), 36.0g polymethyl acrylic acid glycol ester, 60.0g hydroxyethyl methylacrylate, 36.0g vinylbenzene macromole, 3.6g mercaptoethanol, 2.4g azo methyl pentane nitrile and 18g methylethylketone in 2.5 hours.After the dropping, through in flask, dripping the mixing solutions of 0.8g azo methyl pentane nitrile and 18g methylethylketone in 0.5 hour.After 1 hour, add 0.8g azo methyl pentane nitrile, recurring 1 hour 65 ℃ of following slakings.After reaction finishes, add the 364g methylethylketone in flask, preparation 800g concentration is the polymers soln A of 50 quality %.
(Production Example 1-1)
The preparation of-magenta pigment polymer particles water dispersion-
Then, potassium hydroxide aqueous solution, 20g methylethylketone and the 13.6g ion exchanged water of the C.I. pigment red 122 of polymers soln A, the 42g that 28g is obtained, the 1mol/L of 13.6g fully stir, and carry out mixing with roller mill then.The slurry that obtains is put in the 200g pure water, after fully stirring, heated up in a steamer methylethylketone and water, make and contain the water dispersion of magenta pigment polymer particles that 15 quality % pigment, solid substance are the Production Example 1-1 of 20 quality % with vaporizer.
(Production Example 1-2)
The preparation of-green pigment polymer particles water dispersion-
Except in Production Example 1-1, beyond copper phthalocyanine replaced C .I. pigment red 122, prepare the green pigment polymer particles water dispersion of Production Example 1-2 by the mode identical with Production Example 1-1.In addition, making solid substance during preparation is that 20 quality %, pigment colorant are 12 quality %.
(Production Example 1-3)
The preparation of-yellow ultramarine polymer particles water dispersion-
Except in Production Example 1-1, beyond C.I Pigment Yellow 73 74 replaced C .I. pigment red 122s, prepare the yellow polymer particulate water dispersion of Production Example 1-3 by the mode identical with Production Example 1-1.In addition, making solid substance during preparation is that 20 quality %, pigment colorant are 12 quality %.
(Production Example 2)
The preparation of-surface treated pigments dispersion liquid-
With 90g CTBA specific surface area is 150m 2/ g, DBP oil number are that the carbon black of 100ml/100g adds 3 to, in the metabisulfite solution of 000ml 2.5N, stir under 60 ℃ of temperature, speed 300rpm, react 10 hours, carry out oxide treatment.Filter this reaction solution, the carbon black with the sodium hydroxide solution neutralization leaches carries out ultrafiltration again.The carbon black that obtains is carried out washing and drying, and being dispersed in the pure water and making solid substance is 20 quality %, the charcoal blacks dispersion liquid of preparation Production Example 2.
(Production Example 3)
The preparation of-polymer particles dispersion liquid (the silicone based emulsion of vinylformic acid) B-
The 1L flask interior of having equipped mechanical stirrer, thermometer, nitrogen ingress pipe, return line and dropping funnel is fully replaced with nitrogen, add 8.0g ラ テ system Le S-180,350g ion exchanged water then, mix, be warmed up to 65 ℃.After the intensification, add the peroxidized t-butyl perbenzoate of 3.0g as reaction initiator, 1.0g SODIUM ISOVITAMIN C, mix 45g methyl methacrylate, 160g methacrylic acid 2-ethylhexyl, 5g vinylformic acid, 45g butyl methacrylate, 30g cyclohexyl methacrylate, 15g vinyltriethoxysilane, 8.0g ラ テ system Le S-180 and 340g ion exchanged water after 5 minutes, dripped through 3 hours.Then.80 ℃ of following slakings after 2 hours, be cooled to normal temperature and with sodium hydroxide with pH regulator to 7～8.Heat up in a steamer ethanol with vaporizer, regulate moisture, making the 730g solid substance is the polymeric dispersions B solution of the Production Example 3 of 40 quality %.
The median size of the polymeric dispersions B that is obtained is 130nm (measuring down for 23 ℃).The sedimentograph UPA150 that the mensuration of median size uses マ イ Network ロ ト ラ Star Network company to make measures under 500 times dilution ratio.
(embodiment 1)
The preparation of-recording ink-
The ink composite for preparing following prescription, regulate pH after, be that the film filter of 5 μ m filters with mean pore size, make recording ink.
＜printing ink is formed 〉
The polymer particles dispersion that contains copper phthalocyanine of Production Example 1-2 (solid substance=about 20 quality %, all the other are water, the tinting material/resin in the solid substance (mass ratio)=6/4) ... 32 quality %
The vinylformic acid organic silicon emulsion of Production Example 3 [solid substance 40 quality %, all the other are water, volume average particle size 150nm, the second-order transition temperature of resinous principle are-15 ℃ of (rising of differential heat)～-6 ℃ (flex points)] ... 50 quality %
Glycerine as wetting agent ... 3.2 quality %
1,3 butylene glycol as wetting agent ... 2 quality %
As the 2-ethyl-1 of permeate agent, 3-hexylene glycol ... 2 quality %
Fluorine class tensio-active agent (fluorine alternate c atoms several 4～16) ... 1 quality %
Antisepticize and mildew preventive ... 0.05 quality %
The organic pH regulator agent of amine ... 0.6 quality %
Organic silicon emulsion defoamer ... 0.1 quality %
Water ... surplus
In above-mentioned printing ink was formed, (25 ℃) were that (25 ℃) are the permeate agent 2-ethyl-1 of liquid under the wetting agent glycerine, 1,3 butylene glycol, normal temperature of liquid under the normal temperature, and the total content of 3-hexylene glycol and tensio-active agent is 8.2 quality %.They are equivalent to boiling point and are higher than water and are the liquid component of liquid down at 25 ℃.
Water is 64.7 quality %, and (25 ℃) are 88 quality % for the ratio of the water in the composition of liquid under the normal temperature.
(25 ℃) are 3.8 quality % for the content of solid tinting material under the normal temperature.
Resinous principle is to contain resin in the polymer particles dispersion of copper phthalocyanine and the resin in the vinylformic acid organic silicon emulsion, and it adds up to 22.6 quality %.
The total content of resinous principle with respect to the ratio of the total amount of above-mentioned tinting material and above-mentioned resinous principle by [22.6/ (22.6+3.8)] * 100] calculate, be 85 quality %.
In addition, in the resinous principle here, also comprise the resin in the polymer particles dispersion that contains copper phthalocyanine.Following embodiment and comparative example are too.
(embodiment 2)
The preparation of-recording ink-
The ink composite for preparing following prescription, regulate pH after, be that the film filter of 5 μ m filters with mean pore size, make recording ink.
＜printing ink is formed 〉
(solid substance=about 20 quality %, all the other are water to the polymer particles dispersion that contains magenta pigment of Production Example 1-1, the tinting material/resin in the solid substance (mass ratio)=7.5/2.5) ... 32 quality %
The vinylformic acid organic silicon emulsion of Production Example 3 [solid substance 40 quality %, all the other are water, volume average particle size 150nm, the second-order transition temperature of resinous principle are-15 ℃ of (rising of differential heat)～-6 ℃ (flex points)] ... 50 quality %
Glycerine as wetting agent ... 3.2 quality %
1,3 butylene glycol as wetting agent ... 2 quality %
As the 2-ethyl-1 of permeate agent, 3-hexylene glycol ... 2 quality %
Fluorine class tensio-active agent (fluorine alternate c atoms several 4～16) ... 1 quality %
Antisepticize and mildew preventive ... 0.05 quality %
The organic pH regulator agent of amine ... 0.6 quality %
Organic silicon emulsion defoamer ... 0.1 quality %
Water ... surplus
In above-mentioned printing ink was formed, (25 ℃) were that (25 ℃) are the permeate agent 2-ethyl-1 of liquid under the wetting agent glycerine, 1,3 butylene glycol, normal temperature of liquid under the normal temperature, and the total content of 3-hexylene glycol and tensio-active agent is 8.2 quality %.They are equivalent to boiling point and are higher than water and are the liquid component of liquid down at 25 ℃.
Water is 64.7 quality %, and (25 ℃) are 89 quality % for the ratio of the water in the composition of liquid under the normal temperature.
(25 ℃) are 4.8 quality % for the content of solid tinting material under the normal temperature.
Resinous principle is resin in the pigment dispersion and the resin in the vinylformic acid organic silicon emulsion, and it adds up to 21.6 quality %.
The total content of resinous principle with respect to the ratio of the total amount of above-mentioned tinting material and above-mentioned resinous principle by [21.6/ (21.6+4.8)] * 100] calculate, be 82.0 quality %.
(embodiment 3)
The preparation of-recording ink-
The ink composite for preparing following prescription, regulate pH after, be that the film filter of 5 μ m filters with mean pore size, make recording ink.
＜printing ink is formed 〉
The polymer particles dispersion that contains yellow ultramarine of Production Example 1-3 (solid substance=about 20 quality %, all the other are water, the tinting material/resin in the solid substance (mass ratio)=6/4) ... 32 quality %
The vinylformic acid organic silicon emulsion of Production Example 3 [solid substance 40 quality %, all the other are water, volume average particle size 150nm, the second-order transition temperature of resinous principle are-15 ℃ of (rising of differential heat)～-6 ℃ (flex points)] ... 50 quality %
Glycerine as wetting agent ... 3.2 quality %
1,3 butylene glycol as wetting agent ... 2 quality %
As the 2-ethyl-1 of permeate agent, 3-hexylene glycol ... 2 quality %
Fluorine class tensio-active agent (fluorine alternate c atoms several 4～16) ... 1 quality %
Antisepticize and mildew preventive ... 0.05 quality %
The organic pH regulator agent of amine ... 0.6 quality %
Organic silicon emulsion defoamer ... 0.1 quality %
Water ... surplus
In above-mentioned printing ink was formed, (25 ℃) were that (25 ℃) are the permeate agent 2-ethyl-1 of liquid under the wetting agent glycerine, 1,3 butylene glycol, normal temperature of liquid under the normal temperature, and the total content of 3-hexylene glycol and tensio-active agent is 8.2 quality %.They are equivalent to boiling point and are higher than water and are the liquid component of liquid down at 25 ℃.
Water is 64.7 quality %, and (25 ℃) are 89 quality % for the ratio of the water in the composition of liquid under the normal temperature.
(25 ℃) are 3.8 quality % for the content of solid tinting material under the normal temperature.
Resinous principle is resin in the pigment dispersion and the resin in the vinylformic acid organic silicon emulsion, and it adds up to 22.6 quality %.
The total content of resinous principle with respect to the ratio of the total amount of above-mentioned tinting material and above-mentioned resinous principle by [22.6/ (22.6+3.8)] * 100] calculate, be 85.5 quality %.
(embodiment 4)
The preparation of-recording ink-
The ink composite for preparing following prescription, regulate pH after, be that the film filter of 5 μ m filters with mean pore size, make recording ink.
＜printing ink is formed 〉
The carbon black dispersion liquid with hydrophilic radical of Production Example 2 (solid substance 20 quality %, all the other are water, the tinting material/resin in the solid substance (mass ratio)=10/0) ... 30 quality %
The vinylformic acid organic silicon emulsion of Production Example 3 [solid substance 40 quality %, all the other are water, volume average particle size 150nm, the second-order transition temperature of resinous principle are-15 ℃ of (rising of differential heat)～-6 ℃ (flex points)] ... 45 quality %
1,3 butylene glycol as wetting agent ... 5 quality %
2-Pyrrolidone as wetting agent ... 2 quality %
As the 2-ethyl-1 of permeate agent, 3-hexylene glycol ... 2 quality %
Fluorine class tensio-active agent (fluorine alternate c atoms several 4～16) ... 1 quality %
Antisepticize and mildew preventive ... 0.05 quality %
Stablizer ... 0.0005 quality %
Organic pH regulator agent (two kinds) ... 0.65 quality %
Organic silicon emulsion defoamer ... 0.1 quality %
Water ... surplus
In above-mentioned printing ink was formed, (25 ℃) were that (25 ℃) are the permeate agent 2-ethyl-1 of liquid under the wetting agent 1,3 butylene glycol, 2-Pyrrolidone, normal temperature of liquid under the normal temperature, and the total content of 3-hexylene glycol and tensio-active agent is 10 quality %.They are equivalent to boiling point and are higher than water and are the liquid component of liquid down at 25 ℃.
Water is 65 quality %, and (25 ℃) are 87 quality % for the ratio of the water in the composition of liquid under the normal temperature.
(25 ℃) are 6 quality % for the content of solid tinting material under the normal temperature.
Resinous principle is the resin in the vinylformic acid organic silicon emulsion, and its content is 18 quality %.
The total content of resinous principle with respect to the ratio of the total amount of above-mentioned tinting material and above-mentioned resinous principle by [18/ (18+6)] * 100] calculate, be 75 quality %.
In the following manner each recording ink of the embodiment 1～4 that obtains is measured surface tension, pH and viscosity.The results are shown in the table 1.
The mensuration of＜pH 〉
PH is to use pH meter MODEL HM3A (manufacturing of East Asia electric wave Industrial Co., Ltd), measures under 23 ℃.
The mensuration of＜viscosity 〉
Viscosity is to use RE500 type viscometer (Toki Sangyo Co., Ltd.'s manufacturing), adopts awl tube 34 * R24,180rpm, the condition after 3 minutes, measures under 25 ℃.
＜capillary mensuration 〉
Surface tension be to use surface tension apparatus (consonance interface science Co., Ltd. makes, CBVP-Z), the static surface tension that adopts the platinum plate under 25 ℃, to measure.
Table 1
Surface tension (mN/m) pH Viscosity (mpas)
Embodiment 1 24.7 9.28 5.17
Embodiment 2 24.3 9.40 5.49
Embodiment 3 24.2 9.25 5.22
Embodiment 4 24.2 8.95 5.25
＜printing experiment 〉
Use each recording ink that obtains, (company of Ricoh makes, and G707) prints with ink-jet printer.
As paper, (Oji Paper makes the printing that uses common paper (company of Ricoh makes, T6200 paper) and be difficult for absorbing water, POD gloss coating 100g/m 2Paper).For these paper, with dynamic scan imbibition instrumentation fixed duration of contact 1 under the 00ms pure water be 3.1ml/m to the transfer amount of recording medium 2, and pure water is 3.5ml/m to the transfer amount of recording medium under the duration of contact 400ms 2
Its result, for any recording ink, the paper of spreading and sinking in does not all appear in the T6200 paper of making as the company of Ricoh of common paper, the image color height, although and be common paper, still obtained developing the color, not having the image of stain.
In addition,, occur dyeing hardly during with interior wiping, obtained no problem substantially image time of drying back 1 minute of printing for the POD gloss coated paper that is difficult for infiltration.And, POD gloss coating 100g/m 2The image distinctness of paper has obtained the image approaching with print.
(comparative example 1)
The preparation of-recording ink-
The ink composite for preparing following prescription, regulate pH after, be that the film filter of 0.8 μ m filters with mean pore size, make recording ink.
＜printing ink is formed 〉
(solid substance=about 20 quality %, all the other are water to the polymer particles dispersion that contains dimethyl quinoline a word used for translation ketone pigment of Production Example 1-1, the tinting material/resin in the solid substance (mass ratio)=7.5/2.5) ... 33.5 quality %
The vinylformic acid organic silicon emulsion of Production Example 3 [solid substance=about 40 quality %, all the other are water, volume average particle size 150nm, the second-order transition temperature of resinous principle are-15 ℃ of (rising of differential heat)～-6 ℃ (flex points)] ... 25 quality %
Glycerine as wetting agent ... 7.5 quality %
As the 3-methyl isophthalic acid of wetting agent, 3-butyleneglycol ... 22.5 quality %
As the 2-ethyl-1 of permeate agent, 3-hexylene glycol ... 2 quality %
Fluorine class tensio-active agent ... 1 quality %
Antisepticize and mildew preventive ... 0.05 quality %
The organic pH regulator agent of amine ... 0.6 quality %
Organic silicon emulsion defoamer ... 0.1 quality %
Water ... surplus
In above-mentioned printing ink was formed, (25 ℃) were wetting agent glycerine, the 3-methyl isophthalic acid of liquid under the normal temperature, and (25 ℃) are the permeate agent 2-ethyl-1 of liquid under 3-butyleneglycol, the normal temperature, 3-hexylene glycol and tensio-active agent add up to 33 quality %.They are equivalent to boiling point and are higher than water and are the liquid component of liquid down at 25 ℃.
Water is 49.5 quality %, and (25 ℃) are 60 quality % for the ratio of the water in the composition of liquid under the normal temperature.
(25 ℃) are 5 quality % for the content of solid tinting material under the normal temperature.
Resinous principle is resin in the pigment dispersion and the resin in the vinylformic acid organic silicon emulsion, and it adds up to 11.7 quality %.
The total content of resinous principle is 70 quality % with respect to whole solid substances.
(comparative example 2)
The preparation of-recording ink-
The ink composite for preparing following prescription, regulate pH after, be that the film filter of 0.8 μ m filters with mean pore size, make recording ink.
＜printing ink is formed 〉
(solid substance=about 20 quality %, all the other are water to the polymer particles dispersion that contains dimethyl quinoline a word used for translation ketone pigment of Production Example 1-1, the tinting material/resin in the solid substance (mass ratio)=7.5/2.5) ... 54 quality %
The vinylformic acid organic silicon emulsion of Production Example 3 [solid substance is 40 quality %, and all the other are water, and volume average particle size 150nm, the second-order transition temperature of resinous principle are-15 ℃ of (rising of differential heat)～-6 ℃ (flex points)] ... 9 quality %
Glycerine as wetting agent ... 7 quality %
1,3 butylene glycol as wetting agent ... 22.5 quality %
As the 2-ethyl-1 of permeate agent, 3-hexylene glycol ... 2 quality %
Fluorine class tensio-active agent (fluorine alternate c atoms several 4～16) ... 1 quality %
Antisepticize and mildew preventive ... 0.05 quality %
The organic pH regulator agent of amine ... 0.6 quality %
Organic silicon emulsion defoamer ... 0.1 quality %
Water ... surplus
In above-mentioned printing ink was formed, (25 ℃) were that (25 ℃) are the permeate agent 2-ethyl-1 of liquid under the wetting agent glycerine, 1,3 butylene glycol, normal temperature of liquid under the normal temperature, 3-hexylene glycol and tensio-active agent add up to 32.5 quality %.They are equivalent to boiling point and are higher than water and are the liquid component of liquid down at 25 ℃.
Water is 52.3 quality %, and (25 ℃) are 61.7 quality % for the ratio of the water in the composition of liquid under the normal temperature.
(25 ℃) are 8.1 quality % for the content of solid tinting material under the normal temperature.
Resinous principle is resin in the pigment dispersion and the resin in the vinylformic acid organic silicon emulsion, and it adds up to 6.3 quality %.
The total content of resinous principle with respect to the ratio of the total amount of above-mentioned tinting material and above-mentioned resinous principle by [6.3/ (6.3+8.1)] * 100] calculate, be 44 quality %.
(comparative example 3)
The preparation of-recording ink-
The ink composite for preparing following prescription, regulate pH after, be that the film filter of 0.8 μ m filters with mean pore size, make recording ink.
＜printing ink is formed 〉
(solid substance=about 20 quality %, all the other are water to the polymer particles dispersion that contains dimethyl quinoline a word used for translation ketone pigment of Production Example 1-1, the tinting material/resin in the solid substance (mass ratio)=7.5/2.5) ... 74 quality %
Glycerine as wetting agent ... 7 quality %
As the 3-methyl isophthalic acid of wetting agent, 3-butyleneglycol ... 15 quality %
As the 2-ethyl-1 of permeate agent, 3-hexylene glycol ... 2 quality %
Polyoxygenated alkene alkyl ether tensio-active agent (ソ Le one Le EP-5035, Nippon Shokubai Co., Ltd makes) ... 1 quality %
Antisepticize and mildew preventive ... 0.05 quality %
The organic pH regulator agent of amine ... 0.2 quality %
Organic silicon emulsion defoamer ... 0.1 quality %
Water ... surplus
In above-mentioned printing ink was formed, (25 ℃) were wetting agent glycerine, the 3-methyl isophthalic acid of liquid under the normal temperature, and (25 ℃) are the permeate agent 2-ethyl-1 of liquid under 3-butyleneglycol, the normal temperature, 3-hexylene glycol and tensio-active agent add up to 25 quality %.They are equivalent to boiling point and are higher than water and are the liquid component of liquid down at 25 ℃.
Water is 59.9 quality %, and (25 ℃) are 71 quality % for the ratio of the water in the composition of liquid under the normal temperature.
(25 ℃) are 11 quality % for the content of solid tinting material under the normal temperature.
Resinous principle is the resin in the pigment dispersion, is 3.7 quality %.
The total content of resinous principle is 25 quality % with respect to total solid.
(comparative example 4)
The preparation of-recording ink-
The ink composite for preparing following prescription, regulate pH after, be that the film filter of 0.8 μ m filters with mean pore size, make recording ink.
＜printing ink is formed 〉
(solid substance=about 20 quality %, all the other are water to the polymer particles dispersion that contains dimethyl quinoline a word used for translation ketone pigment of Production Example 1-1, the tinting material/resin in the solid substance (mass ratio)=7.5/2.5) ... 29 quality %
The vinylformic acid organic silicon emulsion of Production Example 3 [solid substance=about 40 quality %, all the other are water, volume average particle size 150nm, the second-order transition temperature of resinous principle are-15 ℃ of (rising of differential heat)～-6 ℃ (flex points)] ... 43 quality %
Glycerine as wetting agent ... 6 quality %
As the 3-methyl isophthalic acid of wetting agent, 3-butyleneglycol ... 19 quality %
As the 2-ethyl-1 of permeate agent, 3-hexylene glycol ... 1.7 quality %
Fluorine class tensio-active agent ... 0.85 quality %
Antisepticize and mildew preventive ... 0.05 quality %
Stablizer ... 0.0005 quality %
The organic pH regulator agent of amine ... 0.2 quality %
Organic silicon emulsion defoamer ... 0.1 quality %
Water ... surplus
In above-mentioned printing ink was formed, (25 ℃) were wetting agent glycerine, the 3-methyl isophthalic acid of liquid under the normal temperature, and (25 ℃) are permeate agent 2-Pyrrolidone, the 2-ethyl-1 of liquid under 3-butyleneglycol, the normal temperature, 3-hexylene glycol and tensio-active agent add up to 28 quality %.They are equivalent to boiling point and are higher than water and are the liquid component of liquid down at 25 ℃.
Water is 49 quality %, and (25 ℃) are 64 quality % for the ratio of the water in the composition of liquid under the normal temperature.
(25 ℃) are 4.4 quality % for the content of solid tinting material under the normal temperature.
Resinous principle is resin in the pigment dispersion and the resin in the vinylformic acid organic silicon emulsion, and its content adds up to 18.7 quality %.
The total content of resinous principle is 81 quality % with respect to total solid.
Then, by measuring the surface tension (25 ℃) and the viscosity (25 ℃) of each recording ink of comparative example 1～4 with the same mode of embodiment 1～4.The results are shown in the table 2.
Table 2
Surface tension (mN/m) Viscosity (mPas)
Comparative example 1 25.2 10.8
Comparative example 2 25.7 8.2
Comparative example 3 31.0 7.9
Comparative example 4 26.3 23.2
The printing experiment of＜comparative example 1～4 〉
By the mode same, use each recording ink of comparative example 1～4 to print experiment with embodiment 1～4.Its result compares with embodiment, and (Oji Paper makes, POD gloss coating 100g/m at printing for comparative example 1,2 and 3 printing ink 2Paper) drying property on is poor.Particularly in comparative example 2, when other color with same composition overlaps formation secondary look, can confirm the drying property variation.Can think that this is that the ratio of evaporable water is little in the solvent because quantity of solvent is big.But if comparative example 1 is compared with embodiment 1, though then the drying property on above-mentioned glossy paper is poor, because solid substance is than higher, resin is many, so image is good.If regulate for the printing ink adhesion amount that reduces when printing, then glossy paper also can use.Particularly comparative example 1, because resin, solid substance are many, therefore compares with comparative example 2, and (Oji Paper makes, POD gloss coating 100g/m at above-mentioned printing 2Paper) picture quality on also increases than the picture quality on the common paper.
Relative therewith, solid substance is more than the 20 quality % as embodiment 1～4, and as the ratio of water in the composition of liquid be more than the 85 quality % (promptly, boiling point is higher than water and the composition for liquid is few down at 25 ℃), even the paper of the such difficult suction of coated paper for printing then, rate of drying is also fast, and it is good that image also becomes.Solid substance is many in the comparative example 4, resin ratio in the solid substance is also high, but it is because moistening and ratio is also many, thereby ink viscosity uprises, therefore by mechanical injection become difficulty (still because solid substance is many, the printing ink adhesion amount when regulating printing, manage to keep jetting stability, even above-mentioned glossy paper also can use).In addition, the resin ratio is low in the comparative example 3, so image glossiness and anti-label (マ one カ one) property are poor slightly.
Table 3
Solid substance (quality %) Resin ratio (quality %) in the solid substance The ratio of water (quality %) in the liquid Boiling point is higher than water and 25 ℃ of total amounts (quality %) of descending to the composition of liquid
Embodiment
1 26.4 85 89.0 8.2
Embodiment 2 26.4 82 89.0 8.2
Embodiment 3 26.4 85 89.0 8.2
Embodiment 4 24.0 75 87.0 10.0
Comparative example 1 16.7 70 60.0 33.0
Comparative example 2 14.4 44 62.0 32.5
Comparative example 3 14.8 25 71.0 25
Comparative example 4 23 81 64.0 28
Table 3 shows the components in proportions of embodiment 1～4 and comparative example 1～4.
Table 4
Resin ratio in the solid substance More than the 40 quality % and less than 70 quality % 70～95 quality % Surpass 95 quality %
Fixation performance is poor slightly, and image gloss is poor slightly Photographic fixing, image zero Image color is low
In addition, with regard under 25 ℃ for regard to the solid components in proportions, solid substance ink viscosity for a long time increases.Because the viscosity of printing ink can not be too big, thereby solid substance is 50 quality % at most.The lower limit of solid substance is not particularly limited, and still in order to ensure the concentration of image, 10 quality % are necessary.In addition, be under the situation of lower concentration at wetting agent, in order to make viscosity up to a certain degree, thereby form image preferably, preferred solid substance amount is more than 20 quality.Viscosity is low, the problem when changing the solid substance amount is concluded and is shown in the following table 5.But, particularly when paying attention to spraying reliability, though it is below the 20 quality % that solid substance is also arranged, and the situation of lowering viscousity, but in this case, if moistening dosage (perhaps being the one-tenth component of liquid down at 25 ℃) is below the 20 quality %, then improving for the drying property on the little recording medium of the such water-retaining capacity of above-mentioned recording medium of the present invention has effect.
Table 5
25 ℃ is down the amount that liquid and boiling point are higher than the liquid component of water Surpass 20 quality % 20～15 quality % 3～15 quality % Less than 3 quality %
Solid substance 10～20 quality % The rate of drying of offset paper * (can use when requiring) but underspeed The rate of drying △ of offset paper The rate of drying zero of offset paper Spray reliability △
20～30 quality %
30～50 quality % The mechanical injection difficulty
As shown in table 5, consider that from the rate of drying of offset printing White Board preferred moistening dosage is below the 20 quality %, more preferably below the 15 quality %.But, do not have this restriction not influencing under the slow print speed of exsiccant.On the other hand, if wetting agent quantity not sufficient 3 quality %, solid substance exists the problem of spraying the reliability aspect for a long time.But, be not to use by the various methods of keeping mechanism.
Coated paper for printing herein is meant that for example the POD gloss of Oji Paper's manufacturing is coated with 100g/m 2Paper such, compare the level and smooth paper (not necessarily consistent) that is difficult to absorb water with common ink-jet dedicated paper or common paper with earmarking of manufacturers.These paper do not have ink-jet dedicated paper or the such water-retaining capacity of vellum, for common jetted ink, and its dry time that needs much more very.
＜printing test after stopping using for a long time 〉
Then, (company of Ricoh makes, and G707), prints with each recording ink of embodiment 1～4 to use ink-jet printer.At this moment, make the lid of preserving moisture be closing condition, the water to wherein injecting about 0.1cc stops printing under this state, preserve.Then,, still do not have obstruction, can restart and print even through 3 days.Can confirm that thus it is effective supplying with water when stopping using in the lid of preserving moisture.If in lid, do not inject water, obstruction is arranged when then restarting slightly, but can restore by cleaning.
In addition, (company of Ricoh makes, and G707), prints with each recording ink of embodiment 1～4, stops 1 day then, though cyan, the whole passages of xanchromatic all can print afterwards, pinkish red nozzle has about 10% to stop up to use ink-jet printer.Therefore, the magenta ink that replaces to the many comparative examples 2 of moistening dosage is preserved.After the preservation, when printing with the offset printing White Board, the low wetting agent printing ink that replaces to embodiment 2 prints, and can print this moment, do not go wrong.
By this according to the paper medium with the printing ink that uses as low wetting agent printing ink, the printing ink of employing high-humidity agent concentration during preservation is even also can carry out quick-drying printing for the printing of water-absorbent difference.
In addition, use contains the water of 5 quality % glycerine, 20 quality % butyleneglycols and surplus, and when replacing each recording ink of embodiment 1～4 with the moisture retention liquid that the agent of amine pH regulator is adjusted to pH=9, if change into this moisture retention liquid when stopping using for a long time, then can proceed printing, and can not go wrong.
(embodiment 5)
The preparation of-recording ink-
In embodiment 1, (Shin-Etsu Chemial Co., Ltd makes to change fluorine class tensio-active agent (fluorine alternate c atoms number is 4～16) into polyether-modified silicone based tensio-active agent, goods name: KF-642), in addition, the recording ink for preparing embodiment 5 by the mode identical with embodiment 1.
(embodiment 6)
The preparation of-recording ink-
In embodiment 2, (Shin-Etsu Chemial Co., Ltd makes to change fluorine class tensio-active agent (fluorine alternate c atoms number is 4～16) into polyether-modified silicone based tensio-active agent, goods name: KF-642), in addition, the recording ink for preparing embodiment 6 by the mode identical with embodiment 2.
(embodiment 7)
The preparation of-recording ink-
In embodiment 3, (Shin-Etsu Chemial Co., Ltd makes to change fluorine class tensio-active agent (fluorine alternate c atoms number is 4～16) into polyether-modified silicone based tensio-active agent, goods name: KF-642), in addition, the recording ink for preparing embodiment 7 by the mode identical with embodiment 3.
(embodiment 8)
The preparation of-recording ink-
In embodiment 4, (Shin-Etsu Chemial Co., Ltd makes to change fluorine class tensio-active agent (fluorine alternate c atoms number is 4～16) into polyether-modified silicone based tensio-active agent, goods name: KF-642), in addition, the recording ink for preparing embodiment 8 by the mode identical with embodiment 4.
Each recording ink of the embodiment 5～8 that obtains, all in the scope at 26 ± 2mN/m, viscosity is 5.3 ± 0.4mPas (25 ℃) in the surface tension under 25 ℃ for it.Even these printing ink are through prolonged preservation, surface tension also is difficult for changing.
＜printing experiment 〉
For each recording ink that is obtained, by printing experiment with the same mode of embodiment 1～4.Its result, under the situation of using any printing ink, levelling property is all good, even be coated with 100g/m for the POD gloss of water-absorbent difference 2Paper also can obtain distinct image.Nor there is the problem of drying property aspect.
(embodiment 9)
In embodiment 1, change fluorine class tensio-active agent (fluorine alternate c atoms number is 4～16) the polyoxyethylene tensio-active agent of nonionic class into, in addition, prepare the recording ink of embodiment 9 by the mode identical with embodiment 1.
Each recording ink of the embodiment 9 that obtains, its surface tension under 25 ℃ is 30mN/m, and pH is 9.1, and viscosity is 5.3mPas (25 ℃).
＜printing experiment 〉
For the recording ink that is obtained, by printing experiment with the same mode of embodiment 1～4.Its result though image is good to a certain extent, compares during with silicone based tensio-active agent of use or fluorine class tensio-active agent, and the result is poor slightly.
(comparative example 5)
The preparation of-recording ink-
In embodiment 2, do not add fluorine class tensio-active agent (fluorine alternate c atoms number is 4～16) and permeate agent, in addition, prepare the recording ink of comparative example 5 by the mode identical with embodiment 2.
The recording ink of the comparative example 5 that obtains, its surface tension under 25 ℃ is more than the 40mN/m, and pH is 9.2, and viscosity is 4.8mPas (25 ℃).
＜printing experiment 〉
For the recording ink that obtains, by printing experiment with the same mode of embodiment 1～4.Its result, the surface tension height of printing ink is difficult to soak into nozzle, and therefore printing is unstable.
(comparative example 6)
In embodiment 4, change carbon black dispersion liquid into 55 quality %, the vinylformic acid organic silicon emulsion is become 17 quality %, in addition, prepare recording ink by the mode identical with embodiment 4.In this printing ink, the resin ratio in the solid substance is 38 quality %, and 25 ℃ times the content for the high boiling liquid composition of liquid is 7 quality %.
＜printing experiment 〉
For the recording ink that obtains, by printing experiment with the same mode of embodiment 1～4.Its result, though the rate of drying on printing is fast, because resin is few, tone is not bright-coloured, stability is poor slightly.
(embodiment 10)
The preparation of-printing ink group and ink medium group-
Each printing ink of embodiment 1～4 is made up the printing ink group of preparation embodiment 10.Use this printing ink group and following various paper used for recording, carry out performance evaluation in the following manner.
＜paper used for recording (1) 〉
Commercially available with paper (trade(brand)name: オ one ロ ラ コ one ト, Substance=104.7g/m 2, Jujo Paper Co., Ltd makes)
＜paper used for recording (2) 〉
Oji Paper makes, POD gloss coating 100g/m 2Paper
＜paper used for recording (3) 〉
Commercially available ink-jet dull-finished art paper (trade(brand)name: ス one パ one Off ア イ Application dedicated paper, セ イ コ one エ プ ソ Application Co., Ltd. makes)
For above-mentioned paper used for recording (1)～(3), measure the transfer amount of pure water in the following manner.The results are shown in the table 6.
The transfer amount that＜usefulness dynamic scan imbibition instrumentation is decided water and printing ink 〉
For above-mentioned paper used for recording (1)～(3), use dynamic scan imbibition meter (model: KS350D, consonance Jinggong Co., Ltd makes) to measure the absorption curve of pure water.Absorption curve is to utilize transfer amount (mL/m 2) and the square root  (ms) of duration of contact mapping, form straight line with certain slope, measure transfer value behind the certain hour by interpolation technique.
Table 6
Pure water
Duration of contact 100ms Duration of contact 400ms
Paper used for recording (1) 2.8 3.4
Paper used for recording (2) 3.1 3.5
Paper used for recording (3) 41.0 44.8
Then, use the printing ink group of embodiment 10, and use above-mentioned paper used for recording (1)～(3), printing ink is filled in the ink-jet printer (company of Ricoh makes, IPSiO G707), under GOOD TASTE/high image quality pattern, print as recording medium.
Then, for the image printing thing that obtains, estimate foaming, reflecting feel in the following manner.The results are shown in the table 7.
＜bubble
The foaming degree of all images part that visual observation is green and red is estimated by following standard.
[judgement criteria]
◎: do not produce and bubble, uniformly print.
Zero: can find to bubble a little.
△: find to have tangible foaming to take place.
*: find to have serious foaming to take place.
The evaluation of＜reflecting feel 〉
The reflecting feel degree of visual observation image section is estimated by following standard.
[judgement criteria]
◎: the reflecting feel that height is arranged.
Zero: glossy sense.
*: do not find reflecting feel.
Table 7
The printing ink group of embodiment 10
Bubble Reflecting feel
Paper used for recording (1) ○ ○
Paper used for recording (2) ◎ ○
Paper used for recording (3) ◎ △
(comparative example 7)
The preparation of-printing ink group-
Preparation by the magenta ink of comparative example 2, and except that magenta pigment and the magenta ink of this comparative example 2 copper phthalocyanine) and Yellow ink (pigment: the printing ink group of the comparative example 7 of Gou Chenging C.I. Pigment Yellow 73 74) cyan ink (pigment: of same composition is arranged.
Use the printing ink group of this comparative example 7, on above-mentioned paper used for recording (2), print.With the printing ink adhesion amount of the image section equal extent of the foregoing description 1～4 under when comparing, its drying property is poor, foaming has also taken place in the secondary look.The results are shown in the table 8.
Table 8
The printing ink group of comparative example 7
Bubble Reflecting feel
Paper used for recording (2) △ ○
By the result of table 7 and table 8 as can be known, compare with the printing ink group of comparative example 7, the printing ink group of embodiment 10 can improve picture quality effectively when using the little paper of pure water transfer amount.Paper used for recording (1) and (2), rate of drying is slow under the situation of the printing ink group of comparative example 7, can find to bubble.In addition, if the print after 20 seconds is carried out overlapping, the back side then occurs and stain.In addition, bubbling and back side pickup does not appear in the printing ink group of embodiment 10 substantially.
For the printing ink group of paper used for recording (2) and comparative example 7, can use sometimes, but under identical ink droplet quantity, bubbling does not appear in the printing ink group of embodiment 10 by regulating ink droplet quantity yet.In general, the printing ink group of embodiment 10 duration of contact fixed with utilizing dynamic scan imbibition instrumentation under the 100ms pure water be 2～35ml/m to the transfer amount of recording medium 2, and pure water is 3～40ml/m to the transfer amount of recording medium under the duration of contact 400ms 2The combination of medium be preferred.
And from the reflecting feel of image, more preferably pure water is 2～15ml/m to the transfer amount of recording medium under 100ms duration of contact 2, and pure water is 3～20ml/m to the transfer amount of recording medium under the duration of contact 400ms 2The combination of medium.But, though picture quality is poor slightly, but still service recorder with paper (3).
(embodiment 11)
The ink composite for preparing following prescription, regulate pH after, be that the film filter of 5 μ m filters with mean pore size, make magenta ink A.
The prescription of-magenta ink A-
The polymer particles dispersion that contains dimethyl quinoline a word used for translation ketone pigment of Production Example 1-1 ... 32 quality %
The vinylformic acid organic silicon emulsion of Production Example 3 ... 36 quality %
Glycerine ... 3 quality %
Fluorine class tensio-active agent ... 1 quality %
Antisepticize and mildew preventive ... 0.05 quality %
Amine pH regulator agent ... 0.6 quality %
Organic silicon emulsion defoamer ... 0.1 quality %
Water ... surplus
(embodiment 12)
The prescription of-cyan ink A-
In embodiment 11, the polymer particles dispersion that will contain dimethyl quinoline a word used for translation ketone pigment changes the polymer particles dispersion that contains copper phthalocyanine of Production Example 1-2 into, in addition, prepares the cyan ink A of embodiment 12 by the mode identical with embodiment 11.
(embodiment 13)
The preparation of-Yellow ink A-
In embodiment 11, the polymer particles dispersion that will contain dimethyl quinoline a word used for translation ketone pigment changes the polymkeric substance that contains yellow ultramarine of Production Example 1-3 into, in addition, prepares the Yellow ink A of embodiment 13 by the mode identical with embodiment 11.
(embodiment 14)
The preparation of-magenta ink B-
In embodiment 11, change the content of glycerine into 13 quality %, in addition, prepare the magenta ink B of embodiment 14 by the mode identical with embodiment 11.
(embodiment 15)
The preparation of-cyan ink B-
In embodiment 12, change the content of glycerine into 13 quality %, in addition, prepare the cyan ink B of embodiment 15 by the mode identical with embodiment 12.
(embodiment 16)
The preparation of-Yellow ink B-
In embodiment 13, change the content of glycerine into 13 quality %, in addition, prepare the Yellow ink B of embodiment 16 by the mode identical with embodiment 13.
(embodiment A-1)
The preparation of-magenta ink C-
In embodiment 11, change the content of glycerine into 28 quality %, in addition, prepare the magenta ink C of embodiment A-1 by the mode identical with embodiment 11.
(embodiment A-2)
The preparation of-cyan ink C-
In embodiment 12, change the content of glycerine into 28 quality %, in addition, prepare the cyan ink C of embodiment A-2 by the mode identical with embodiment 12.
(embodiment A-3)
The preparation of-Yellow ink C-
In embodiment 13, change the content of glycerine into 28 quality %, in addition, prepare the Yellow ink C of embodiment A-3 by the mode identical with embodiment 13.
Then, by the mode identical, measure the surface tension and the viscosity of each recording ink of embodiment 11～16 and embodiment A-1～A-3 with the foregoing description 1～4.The results are shown in the table 9.
Table 9
Printing ink Surface tension (mN/m) Viscosity (mPas)
Embodiment 11 Magenta ink A 24.6 3.03
Embodiment 12 Cyan ink A 24.5 2.78
Embodiment 13 Yellow ink A 24.7 2.85
Embodiment 14 Magenta ink B 24.5 4.41
Embodiment 15 Cyan ink B 24.3 4.0
Embodiment 6 Yellow ink B 24.3 4.1
Embodiment A-1 Magenta ink C 23.5 8.71
Embodiment A-2 Cyan ink C 23.7 8.07
Embodiment A-3 Yellow ink C 23.5 8.26
In addition, in embodiment 11～16 and embodiment A-1～A-3, calculate the ratio of water in resin ratio in solid substance amount, the solid substance, the liquid and the total amount of liquid component.The results are shown in the table 10.In addition, be higher than the calculating of the liquid of water, count the fluorine class tensio-active agent beyond the wetting agent herein for boiling point.
Table 10
Printing ink Solid substance (quality %) Resin ratio (quality %) in the solid substance The ratio of water (quality %) in the liquid Boiling point is higher than water and 25 ℃ of total amounts (quality %) of descending to the composition of liquid
Embodiment
11 Pinkish red A 20.8 77 95 4
Embodiment 14 Pinkish red B 20.8 77 82 14
Embodiment A-1 Pinkish red C 20.8 77 63 29
Embodiment 12 Cyan A 20.8 82 95 4
Embodiment 15 Cyan B 20.8 82 82 14
Embodiment A-2 Cyan C 20.8 82 63 29
Embodiment 13 Yellow A 20.8 82 95 4
Embodiment 16 Yellow B 20.8 82 82 14
Embodiment A-3 Yellow C 20.8 82 63 29
The content of the wetting agent that embodiment A-1, A-2 and A-3 are such is that the recording ink of 29 quality % is compared with the recording ink below the humectant content of embodiment 11～16 is 20 quality %, the injection reliability excellence after the long-term placement of nozzle.But, particularly since with dynamic scan imbibition instrumentation fixed duration of contact under the 100ms pure water be 2～35ml/m to the transfer amount of recording medium 2, and pure water is 3～40ml/m to the transfer amount of recording medium under the duration of contact 400ms 2Recording medium slow to the absorption rate of printing ink, therefore if the content of wetting agent is many, then the rate of drying of the image behind the record is slack-off.
If attention rate of drying, then the content with wetting agent reduces to below the 20 quality %, spray reliability with following method correspondence: when stopping ink-vapor recording for a long time, substitute recording ink with moisture retention liquid, when restarting ink-vapor recording, substitute the ink jet recording method of moisture retention liquid and when stopping ink-vapor recording for a long time, in the cladding system that covers the record-header nozzle, supply with the method for moisture retention liquid with recording ink.
On the other hand, pay attention to spraying under the situation of reliability, increase the content of wetting agent, for the low paper of aforesaid absorption of inks speed, in order to prevent to stain, take to increase the time of drying after the printing or the method for compulsory drying installation is set because of drying makes overlapping causing of document image slowly.
Compare with printing ink in the past, it is in order to make tinting material residual on paper to improve image color that the amount of solid substance is increased to more than the 20 quality %.If the solid substance amount is many like this, because reliability variation, therefore not only to increase the content of wetting agent, even and the solid substance amount many, also must use and in the higher polymer particles of reliability, contain water insoluble or be insoluble in the colorant of water and the pigment of the polymer emulsion type that obtains.In addition, how the solid substance amount also helps to improve drying property.
On the other hand, increase ratio as the glycerine of wetting agent, be because glycerine and other wetting agent to compare the equilibrium water component high, can suppress moisture evaporation speed, and can suppress solidifying of the dried printing ink of printing ink.
In addition, even add the wetting agent of same amount, glycerine has the advantage that the viscosity that can not make printing ink increases as other solvent.
In fact the above fact is confirmed by experiment.
In addition, with dynamic scan imbibition instrumentation fixed duration of contact under the 100ms pure water be 2～35ml/m to the transfer amount of above-mentioned recording medium 2, and pure water is 3～40ml/m to the transfer amount of above-mentioned recording medium under the duration of contact 400ms 2Recording medium because to cover the ability of tinting material more intense, therefore in order to improve image color, tinting material must be retained in the surface.Therefore, under the situation of dye ink, tinting material invades inside, does not almost have image color.For such recording medium, make high resin concentration and high solid concentration by making pigment ink, tinting material is retained on the recording medium, the image color excellence.
Increased under the situation of recording ink of humectant content,, the forced drying operation has been set preferably in order to improve rate of drying.As drying means, can be that drying process is set before record, also can be in the method for drying process any is set behind record.
As drying installation, can be to use microwave energy to give the device of microwave energy to paper, also can be the so contactless device of heater strip mode.The device (for example warming mill) of contact can also be set in addition, in addition.Directly pair roller heating itself, perhaps also can by other thermals source indirectly pair roller heat.
In addition, the image sample after being printed on one side heats similarly, can carry out double-sided copying then.Before record when carrying out drying, can prevent that ink dot drying because of document image from causing slowly to be called as the blistered density unevenness that is caused by the liquid local derviation even.When after record, carrying out drying, the curling comparatively difficulty that becomes of paper.In addition, less to the influence of printer main body.
(Embodiment B-1)
The recording ink for preparing following prescription.
The polymer particles dispersion that contains copper phthalocyanine of Production Example 1-2 (solid substance=about 20 quality %, all the other are water, the tinting material/resin in the solid substance (mass ratio)=6/4) ... 38 quality %
Vinylformic acid organic silicon emulsion [solid substance 40 quality % with Production Example 3, all the other are water, volume average particle size 150nm, the second-order transition temperature of resinous principle are-15 ℃ of (rising of differential heat)～-6 ℃ (flex points)] concentrate, making solid substance is the material of 55 quality % ... 36 quality %
1,3 butylene glycol as wetting agent ... 19 quality %
Glycerine as wetting agent ... 6 quality %
Fluorine class tensio-active agent (fluorine alternate c atoms several 4～16) ... 1 quality %
Antisepticize and mildew preventive ... 0.05 quality %
The organic pH regulator agent of amine ... 0.6 quality %
Organic silicon emulsion defoamer ... 0.1 quality %
Water ... surplus
The recording ink of this Embodiment B-1 is that humectant content is that 25 quality %, total solid are the high solid substance cyan ink of 26 quality %.
(Embodiment B-2)
In Embodiment B-1, the polymer particles dispersion of the oil-containing copper phthalocyanine of Production Example 1-2 is changed into the polymer particles dispersion that contains dimethyl quinoline a word used for translation ketone pigment of Production Example 1-1, in addition, preparing humectant content by the mode identical with Embodiment B-1 is that 25 quality %, total solid are the high solid substance magenta ink of 26 quality %.
(Embodiment B-3)
In Embodiment B-1, the polymer particles dispersion of the oil-containing copper phthalocyanine of Production Example 1-2 is changed into the polymer particles dispersion that contains yellow ultramarine of Production Example 1-3, in addition, preparing humectant content by the mode identical with Embodiment B-1 is that 25 quality %, total solid are the high solid substance cyan ink of 26 quality %.
Then, by the method identical, measure the viscosity of each recording ink under 25 ℃ of Embodiment B-1～B-3 with the foregoing description 1.The results are shown in the table 11.
Table 11
Viscosity (mPas)
Embodiment B-1 12.8
Embodiment B-2 12.3
Embodiment B-3 15.2
(Embodiment C-1～C-3)
In Embodiment B-1～B-3, with the content of colorant dispersion change into 42 quality %, with the content of vinylformic acid organic silicon emulsion change into 42 quality %, will be as 1 of wetting agent, the content of 3-butyleneglycol changes 11 quality % into, changes the content of glycerine into 4 quality %, and the preparation humectant content is that 15 quality %, total solid are cyan, the magenta of 31 quality %, the recording ink of xanchromatic Embodiment C-1～C-3.
Then, by the method identical, measure the viscosity of each recording ink under 25 ℃ of Embodiment C-1～C-3 with the foregoing description 1.The results are shown in the table 12.
Table 12
Viscosity (mPas)
Embodiment C-1 12.5
Embodiment C-2 11.7
Embodiment C-3 12.8
Embodiment C-1～C-3 makes the solid substance amount quite a lot of, and the content of wetting agent is suppressed at 15 quality %, and Embodiment B-1～B-3 is suppressed at 26 quality % with the solid substance amount, and to make the content of its wetting agent be 25 quality %.
The solid substance amount of any one is more than the 20 quality %, and is quite high, and therefore (company of Ricoh makes, and T6200) image color on is all very high, and ink bleed is also few, is preferable image (with reference to Figure 19) in common paper.On the other hand, even the printing ink of so high solid concentration, owing to being contains water insoluble in polymer particles or be insoluble in the pigment of the polymer emulsion type that the colorant of water obtains, it is good therefore to spray reliability.But, the solid substance of Embodiment C-1～C-3 is that the content of 31 quality %, wetting agent is that the printing ink of 15 quality % is because the solid substance amount is very high, place the back and produce spray nozzle clogging sometimes at the record initial stage, but the humectant content of Embodiment B-1～B-3 is the printing ink of 25 quality %, although its solid substance is 26 quality %, be quite high solid substance, but jetting stability.In addition, as ink-jet printer, the G707 that uses company of Ricoh to make.
On the other hand, estimate the POD gloss coating 100g/m that makes in Oji Paper 2Drying property during the enterprising line item of paper.
Compare with Embodiment C-1～C-3, the time of drying of Embodiment B-1～B-3 that humectant content is many is long.Figure 20 illustrates the adhesion amount of green part on the spot and the figure of the relation that filter paper adheres to time of drying.
Before record, this POD gloss is coated with 100g/m with drying machine 2Paper heating is carried out record with the recording ink of Embodiment C-1～C-3.
As a result, shorten to below 1/2 time of drying.Adopting commercially available heating roller drier to carry out drying after adopting drying machine to heat, write down in record can improve time of drying significantly.
Even the printing ink of so high solid concentration is more than the 25 quality % by the content that makes wetting agent, increased the injection reliability, if at POD gloss coating 100g/m 2Directly carry out record on the low paper of the such absorption of inks ability of paper, because the content of wetting agent is many, time of drying is elongated, makes it dry but before and after record paper heated, and then can realize high-speed record.
(embodiment D-1)
The recording ink for preparing following prescription.
The polymer particles dispersion that contains copper phthalocyanine of Production Example 1-2 (solid substance=about 20 quality %, all the other are water, the tinting material/resin in the solid substance (mass ratio)=6/4) ... 45 quality %
The vinylformic acid organic silicon emulsion of Production Example 3 [solid substance 40 quality %, all the other are water, volume average particle size 150nm, the second-order transition temperature of resinous principle are-15 ℃ of (rising of differential heat)～-6 ℃ (flex points)] ... 10 quality %
1,3 butylene glycol as wetting agent ... 24 quality %
Glycerine as wetting agent ... 8 quality %
Fluorine class tensio-active agent (fluorine alternate c atoms several 4～16) ... 1 quality %
Antisepticize and mildew preventive ... 0.05 quality %
The organic pH regulator agent of amine ... 0.6 quality %
Organic silicon emulsion defoamer ... 0.1 quality %
Water ... surplus
The recording ink of this embodiment D-1 is that humectant content is that 32 quality %, total solid are the high solid substance cyan ink of 13 quality %.
(embodiment D-2)
In embodiment D-1, the polymer particles dispersion that contains copper phthalocyanine of Production Example 1-2 is changed into the polymer particles dispersion that contains dimethyl quinoline a word used for translation ketone pigment of Production Example 1-1, in addition, preparing humectant content by the mode identical with embodiment D-1 is that 32 quality %, total solid are the high solid substance magenta ink of 13 quality %.
(embodiment D-3)
In embodiment D-1, the polymer particles dispersion of the oil-containing copper phthalocyanine of Production Example 1-2 is changed into the polymer particles dispersion that contains yellow ultramarine of Production Example 1-3, in addition, preparing humectant content by the mode identical with embodiment D-1 is that 32 quality %, total solid are the high solid substance cyan ink of 13 quality %.
Then, by the method identical, measure the viscosity of each recording ink under 25 ℃ of embodiment D-1～D-3 with the foregoing description 1.The results are shown in the table 13.
Table 13
Viscosity (mPas)
Embodiment D-1 8.17
Embodiment D-2 8.03
Embodiment D-3 8.65
(embodiment E-1～E-3)
In embodiment D-1～D-3, will all change glycerine into as the 1,3 butylene glycol of wetting agent, in addition, prepare the recording ink of cyan, magenta, xanchromatic embodiment E-1～E-3 by the mode identical with embodiment D-1～D-3.
Then, by the method identical, measure the viscosity of each recording ink under 25 ℃ of embodiment E-1～E-3 with the foregoing description 1.The results are shown in the table 14.
Table 14
Viscosity (mPas)
Embodiment E-1 6.76
Embodiment E-2 6.61
Embodiment E-3 6.91
As shown in Table 14, if change wetting agent into glycerine,, and make the high solid substanceization of printing ink easily even identical humectant content also can suppress ink viscosity very low.
In addition, under the environment under the wind of the air regulator of 23 ℃ of humidity 53%RH, temperature, various printing ink are taken out 0.5g be put in the table ware, obtain steam output.
It is slow slightly as the water velocity of evaporation at the initial stage of the recording ink of the embodiment E-1～E-3 of wetting agent only to comprise glycerine, is producing suitable difference (with reference to Figure 21) through steam output behind the certain hour.This is because embodied on the velocity of evaporation that do not coexist of the equilibrium water component of wetting agent.Like this, by increasing amount, play effect, under the situation of particularly high solid substance printing ink, can prevent the curing that the drying of printing ink causes, thereby improve reliability greatly for lowering viscousity, anti-sealing evaporation as the glycerine of wetting agent.
Table 15
The total amount of the composition of liquid Printing ink
Embodiment 17 Printing ink group A 4 quality % Pinkish red A Cyan A Yellow A
Embodiment 18 Printing ink group B 14 quality % Pinkish red B Cyan B Yellow B
Comparative example 10 Printing ink group C 29 quality % Pinkish red C Cyan C Yellow C
Use the printing ink group A～C shown in the table 15, (company of Ricoh makes, and G707) (Oji Paper makes, POD gloss coating 100g/m at glossy paper with ink-jet printer 2Paper) print on.
The printing ink adhesion amount of this moment and the relation of time of drying are shown among Figure 13.For time of drying, on whole 1cm square, print, push filter paper after the printing, the value in the moment that the adhesion amount on the filter paper is reduced is significantly estimated the relation with the ink printing adhesion amount as time of drying.
Time of drying is relevant with the amount (major part is a wetting agent glycerine) that the boiling point under 25 ℃ is higher than the liquid of water as can be known.When the printing ink adhesion amount must be 20g/m 2The time, in order to reach 1 minute with inner drying, the wetting agent (comprising fluorine class tensio-active agent) among the preferred printing ink group C is in shortage, is necessary for below the 20 quality %.But this is comparatively speaking after all, if printing time can be enough slow, also has no relations even then wetting agent is more.
By above result as can be known, when the little paper of this water permeate of glossy paper is carried out ink jet printing, particularly the printing ink adhesion amount of per unit area for a long time, evaporation of water speed works.
In this case, dry enough fast in order to make, moistening dosage is the smaller the better.This has the different of essence with the thinking methods of only considering the decision infiltration rate in the ink jet printing of the super infiltration class of low surface tension in the past.On the other hand, think that the solid substance amount is many more, the amount of liquid that surpasses tolerance is few more, and drying property is good more, if but increase the solid substance amount under similar circumstances at moistening dosage, it is residual that then wetting agent+balance contains the water section appearance, the drying property variation.In a word, can think that moistening dosage works to drying property,, exist the best of breed of solid substance amount, moistening dosage for drying property.
For the mechanism that proves that the evaporation of this water is worked to drying, need to confirm that the water evaporation is actually produces under this speed.
Figure 14 is to use printing ink group C, directly is determined at the graphic representation of the printing ink velocity of evaporation after the printing on the glossy paper by whole green portion.Figure 15 is the graphic representation of the integration of this steam output.Adhere to time of drying about filter paper, reduce significantly and need about 1 minute though filter paper adheres to quantity of ink, reaching filter paper does not have fully to adhere to approximately and needs 3.5 minutes.Be about 70% integration steam output of the finally moisture evaporated amount obtained by the equilibrium moisture content of glycerine under this time, it is very relevant that the water evaporation quantity that shows printing ink and the filter paper of printing ink adhere to time of drying.
Like this, for the low glossy paper of water-retaining capacity, the printing ink evaporation is also very relevant with drying property, even the printing ink of the super infiltration of low surface tension also will be considered the influence of the water evaporation of printing ink to the drying property under the glossy paper situation.Therefore, can think that moistening dosage is very relevant with drying property under the glossy paper situation.
(embodiment 19)
The preparation of-magenta ink-
The magenta ink for preparing following composition.
The polymer particles dispersion that contains magenta pigment of Production Example 1-1 (solid substance 20 quality %) ... 32 quality %
The emulsion resin aqueous solution of Production Example 3 (solid substance 40 quality %) ... 36 quality %
Glycerine ... 3 quality %
(DuPont company makes fluorine class tensio-active agent, FS-300) ... 2.5 quality %
Antisepticize and mildew preventive (ゼ ネ カ company makes, プ ロ キ セ Le LV) ... 0.05 quality %
Amine pH regulator agent ... 0.6 quality %
Silicone based defoamer ... 0.1 quality %
Water ... surplus
To the magenta ink that obtains, when measuring by the mode identical with the foregoing description 1, its viscosity is 3.03mPas, and surface tension is 24.8mN/m.In addition, the total solid in the printing ink is 21 quality %, and all amount of resin is 77 quality % in the solid substance.
(embodiment 20)
The preparation of-cyan ink-
Except the polymer particles dispersion that contains copper phthalocyanine that the dispersion among the embodiment 19 is changed into Production Example 1-2, prepare cyan ink by the mode identical with embodiment 19.
To the cyan ink that obtains, when measuring by the mode identical with the foregoing description 1, its viscosity is 2.78mPas, and surface tension is 24.3mN/m.In addition, the total solid in the printing ink is 21 quality %, and all amount of resin is 82 quality % in the solid substance.
(embodiment 21)
The preparation of-Yellow ink-
Except the polymer particles dispersion that contains monoazo yellow pigment that the dispersion among the embodiment 19 is changed into Production Example 1-3, prepare Yellow ink by the mode identical with embodiment 19.
To the Yellow ink that obtains, when measuring by the mode identical with the foregoing description 1, its viscosity is 2.85mPas, and surface tension is 24.7mN/m.In addition, the total solid in the printing ink is 21 quality %, and all amount of resin is 82 quality % in the solid substance.
(embodiment 22)
The preparation of-magenta ink-
Glycerol content in making embodiment 19 is the 13 quality %, prepares magenta ink by the mode identical with embodiment 19.
To the magenta ink that obtains, when measuring by the mode identical with the foregoing description 1, its viscosity is 4.41mpas, and surface tension is 24.5mN/m.In addition, the total solid in the printing ink is 21 quality %, and all amount of resin is 77 quality % in the solid substance.
(embodiment 23)
The preparation of-cyan ink-
Glycerol content in making embodiment 20 is the 13 quality %, prepares cyan ink by the mode identical with embodiment 20.
To the cyan ink that obtains, when measuring by the mode identical with the foregoing description 1, its viscosity is 4.00mPas, and surface tension is 24.6mN/m.In addition, the total solid in the printing ink is 21 quality %, and all amount of resin is 82 quality % in the solid substance.
(embodiment 24)
The preparation of-Yellow ink-
Glycerol content in making embodiment 21 is the 13 quality %, prepares Yellow ink by the mode identical with embodiment 21.
To the Yellow ink that obtains, when measuring by the mode identical with the foregoing description 1, its viscosity is 4.1mPas, and surface tension is 24.3mN/m.In addition, the total solid in the printing ink is 21 quality %, and all amount of resin is 82 quality % in the solid substance.
(embodiment 25)
The preparation of-magenta ink-
Glycerol content in making embodiment 19 is the 28 quality %, prepares magenta ink by the mode identical with embodiment 19.
To the magenta ink that obtains, when measuring by the mode identical with the foregoing description 1, its viscosity is 8.71mPas, and surface tension is 24.1mN/m.In addition, the total solid in the printing ink is 21 quality %, and all amount of resin is 77 quality % in the solid substance.
(embodiment 26)
The preparation of-cyan ink-
Glycerol content in making embodiment 20 is the 28 quality %, prepares cyan ink by the mode identical with embodiment 20.
To the cyan ink that obtains, when measuring by the mode identical with the foregoing description 1, its viscosity is 8.07mPas, and surface tension is 23.8mN/m.In addition, the total solid in the printing ink is 21 quality %, and all amount of resin is 82 quality % in the solid substance.
(embodiment 27)
The preparation of-Yellow ink-
Glycerol content in making embodiment 21 is the 28 quality %, prepares Yellow ink by the mode identical with embodiment 21.
To the Yellow ink that obtains, when measuring by the mode identical with the foregoing description 1, its viscosity is 8.26mPas, and surface tension is 23.5mN/m.In addition, the total solid in the printing ink is 21 quality %, and all amount of resin is 82 quality % in the solid substance.
Then, for the printing ink group of embodiment 19～21 (printing ink group I), embodiment 22～24 (printing ink group II) and embodiment 25～27 (printing ink group III), (G-707, company of Ricoh makes) prints with ink-jet printer, carries out following evaluation.
As recording medium, use that (eastern レ Co., Ltd. makes trade(brand)name: Le ミ ラ one 75-T60) be cut into the A4 size and the material that obtains with polyester film.
＜polyester film printing evaluation-drying property estimates 1 〉
Will be by 2mm 2The image on the spot of secondary look (green, red, indigo plant) arrange at interval the image that forms in length and breadth by 0.3mm and print by various patterns, stick the filter paper 5A of ア De バ Application テ Star Network company at image section, the time that will reach non-cohesive filter paper is as the dry concluding time.
As a result, for printing ink group I, even with adhesion amount 20g/m 2Pattern carry out ink printing (secondary look-green), become in the time of 150 seconds and do not adhere to filter paper.In addition, even for rubber, refer to touch, enough fixation performances are arranged also.Image section seems to have the concentration of homogeneous on the spot.When relating to literal, also can obtain to have distinctness and the good literal of fixation performance.
On the other hand, for printing ink group II, even at adhesion amount 8g/m 2About under such a spot of situation, surpass and also do not finish drying after 20 minutes.In addition, the time of drying of printing ink group III is longer.In addition, for rubber, refer to touch, fixation performance reached good need more than 1 day.
But,, can not use according to purpose even printing ink group II, III also have raising through fixation performance after a few days.
In addition, if increase the drying process that utilizes moisture eliminator, microwave oven, then printing ink group II, III also can finish drying at short notice.
＜polyester film printing evaluation-drying property estimates 2 〉
Image on the spot in the drying property evaluation 1 is replaced with 1cm 2Image on the spot print and the drying property evaluation.As a result, for printing ink group I, press adhesion amount 20g/m 2Though drying occurs from peripheral part when printing, need more than 5 minutes to centre portions is dry.And centre portions and foursquare diagonal become the high part of image color.
For fear of this problem, when and where is staggered, print 2mm successively 2Image section on the spot, thereby obtained quite uniformly image on the spot.
The printing evaluation of＜glossy paper 〉
The POD gloss coating 100g/m that makes in Oji Paper 2Print on the paper.This paper with dynamic scan imbibition instrumentation fixed duration of contact under the 100ms pure water be 3.1ml/m to the transfer amount of recording medium 2, and pure water is 3.5ml/m to the transfer amount of recording medium under the duration of contact 400ms 2
The time of drying separately of printing ink group I, II, III as shown in figure 16.
For the lower printing glossy paper of this water-absorbent, also to show drying property poor because of moistening dosage (glycerine).Though picture quality is all good, the printing ink adhesion amount for a long time, as the many printing ink of this wetting agent of printing ink group III, Bu Fen image section is prone to gradation unequal (being called foaming) on the spot.
The printing evaluation of＜common paper 〉
The common paper of using company of Ricoh to make, trade(brand)name T6200 prints.
Under the situation of common paper, back side concentration height hinders double-sided replication, but as Figure 17 and shown in Figure 180, is the printing ink group I of 3 quality % for glycerol content, and compared with surface concn, back side concentration is low, has reached the picture quality of suitable double-sided replication.
(comparative example 9～11)
In each printing ink of embodiment 19～21, making the addition of the emulsion resin aqueous solution (solid substance 40 quality %) of Production Example 3 is 10 quality %, in addition, prepares each printing ink of comparative example 9～11 by the mode identical with embodiment 19～21.
In each printing ink that obtains, whole solid substances of printing ink are 10 quality %, and all the resin ratio in the solid substance is 54 quality % (magenta)～63 ink quality % (cyan, yellow).
Then, for each printing ink of the comparative example 9～11 that is obtained, when printing on polyester film, because all solid substance is few, therefore dry slow, because the resin ratio in the solid substance is few, so fixation performance is poor, and image is not distinct yet.
Also have, when in embodiment 25～27, making the addition of the emulsion resin aqueous solution (solid substance 40 quality %) of Production Example 3 be 10 quality % (glycerol content is 28 quality %), also obtained same result.
(comparative example 12)
The following surface of pigments promoting agent dispersion liquid of forming of preparation.
With 100g C.I pigment Blue 15: 3,24.8g polyoxyethylene oleyl ether ammonium sulfate, 175.2g pure water mix, disperse with the wet type sand mill then, interpolation 414.3g pure water also mixes, apply centrifugal treating and remove oversize particle, make contain 14 quality % pigment, solid substance is the green pigment dispersion liquid of 17.5 quality %.
Then, replace green pigment dispersion among the embodiment 20 with the above-mentioned surface of pigments promoting agent dispersion liquid made, in addition, by the mode identical, preparation cyan ink with embodiment 20.
In the cyan ink that obtains, solid substance is 20 quality %, and resin ratio is 78 quality % in the solid substance, and humectant content is 4 quality %.
The cyan ink that obtains is the few tensio-active agent colo(u)rant dispersion printing ink of moistening dosage, and its jetting stability is poor.
(embodiment 28)
The preparation of-magenta ink-
The magenta ink for preparing following composition.
The pinkish red dispersion of Production Example 1-1 (solid substance 20 quality %) ... 32 quality %
The emulsion of Production Example 3 (solid substance 40 quality %) ... 50 quality %
1,3 butylene glycol ... 2 quality %
Glycerine ... 3 quality %
2-ethyl-1,3-hexylene glycol ... 2 quality %
Fluorine class tensio-active agent ... 1 quality %
The organic pH regulator agent of amine ... 0.6 quality %
Silicone based defoamer ... 0.1 quality %
Antisepticize and mildew preventive ... 0.05 quality %
Water ... surplus
For the magenta ink that obtains, when measuring by the mode identical with the foregoing description 1, its viscosity is 5.49mPas, and surface tension is 24.3mN/m.In addition, the solid substance in the printing ink is 26 quality %, and the ratio of resin is 82 quality % in the solid substance, and humectant content is 5 quality % (the liquid component sum that the boiling point under 25 ℃ is higher than water is 8 quality %).
(embodiment 29)
The preparation of-cyan ink-
Except the pinkish red dispersion among the embodiment 28 being changed into the cyan dispersion of Production Example 1-2, prepare cyan ink by the mode identical with embodiment 28.
For the cyan ink that obtains, when measuring by the mode identical with the foregoing description 1, its viscosity is 5.17mPas, and surface tension is 24.7mN/m.In addition, the solid substance in the printing ink is 26 quality %, and the ratio of resin is 86 quality % in the solid substance, and humectant content is 5 quality % (the liquid component sum that the boiling point under 25 ℃ is higher than water is 8 quality %).
(embodiment 30)
The preparation of-Yellow ink-
Except the cyan dispersion among the yellow dispersion replacement embodiment 29 that uses Production Example 1-3, (Shin-Etsu Chemial Co., Ltd makes with polyether-modified silicone based tensio-active agent, goods name: KF-642) replace outside the fluorine class tensio-active agent, prepare Yellow ink by the mode identical with embodiment 29.
For the Yellow ink that obtains, when measuring by the mode identical with the foregoing description 1, its viscosity is 5.22mPas, and surface tension is 25.2mN/m.In addition, the solid substance in the printing ink is 26 quality %, and the ratio of resin is 86 quality % in the solid substance, and humectant content is 5 quality % (the liquid component sum that the boiling point under 25 ℃ is higher than water is 8 quality %).
As each printing ink of the above embodiments 28～30, owing to have the low moistening dosage identical with each printing ink of embodiment 19～21, so when using polyester film as recording medium, fast drying.
(embodiment 31)
The preparation of-magenta ink-
The printing ink for preparing following composition.
The pinkish red dispersion of Production Example 1-1 (solid substance 20 quality %) ... 42 quality %
The resin emulsion of Production Example 3 is concentrated, and making solid substance is the material (solid substance 55 quality %) of 55 quality % ... 42.8 quality %
1,3 butylene glycol ... 11.5 quality %
Glycerine ... 3.8 quality %
2-ethyl-1,3-hexylene glycol ... 1 quality %
Fluorine class tensio-active agent ... 2 quality %
The organic pH regulator agent of amine ... 0.6 quality %
Silicone based defoamer ... 0.1 quality %
Antisepticize and mildew preventive ... 0.05 quality %
Water ... surplus
(embodiment 32)
The preparation of-cyan ink-
Except the cyan dispersion (solid substance is 20 quality %) that the dispersion among the embodiment 31 is changed into Production Example 1-2, prepare cyan ink by the mode identical with embodiment 31.
(embodiment 33)
The preparation of-Yellow ink-
Except the yellow dispersion (solid substance is 20 quality %) that the dispersion among the embodiment 31 is changed into Production Example 1-3, prepare Yellow ink by the mode identical with embodiment 31.
(embodiment 34)
The preparation of-magenta ink-
Except the amount with the pigment dispersion among the embodiment 31 (solid substance is 20 quality %) change into 38 quality %, with emulsion change 36.3 quality % into, with 1, the content of 3-butyleneglycol changes 19.3 quality % into, changes glycerol content into 6.5 quality %, in addition, prepare magenta ink by the mode identical with embodiment 31.
(embodiment 35)
The preparation of-cyan ink-
Except the amount with the pigment dispersion among the embodiment 32 (solid substance is 20 quality %) change into 38 quality %, with emulsion change 36.3 quality % into, with 1, the content of 3-butyleneglycol changes 19.3 quality % into, changes glycerol content into 6.5 quality %, in addition, prepare cyan ink by the mode identical with embodiment 32.
(embodiment 36)
The preparation of-Yellow ink-
Except the amount with the pigment dispersion among the embodiment 33 (solid substance is 20 quality %) change into 38 quality %, with emulsion change 36.3 quality % into, with 1, the content of 3-butyleneglycol changes 19.3 quality % into, changes glycerol content into 6.5 quality %, in addition, prepare Yellow ink by the mode identical with embodiment 33.
Below, for each printing ink, measure viscosity and surface tension by the mode identical with embodiment 1, the results are shown in the table 16.In addition, the solid substance amount of printing ink, the resin ratio in the solid substance, moistening dosage are shown in (liquid component that the boiling point under 25 ℃ is higher than water is 18.3 quality % (embodiment 31～33) and 29.1 quality % (embodiment 34～36)) in the following table 16.
Table 16
Solid substance amount (quality %) Amount of resin in the solid substance (quality %) Moistening dosage (quality %) Viscosity (25 ℃, mPas) Surface tension (25 ℃, mN/m)
Embodiment 31 31 82 15.3 11.8 25.1
Embodiment 32 31 85 15.3 12.5 25.1
Embodiment 33 31 85 15.3 12.9 25.3
Embodiment 34 26.5 81 25.8 12.3 25.1
Embodiment 35 26.3 84 25.8 12.8 25.2
Embodiment 36 26.3 84 25.8 15.2 25.2
Use each printing ink of embodiment 31～33, (company of Ricoh makes, and G-707) prints with ink-jet printer.As recording medium, use that (eastern レ Co., Ltd. makes trade(brand)name: Le ミ ラ one 75-T60) be cut into the A4 size and the material that obtains with polyester film.
With each printing ink of embodiment 31～33 under the square green situation that part is printed on the spot of 1cm, during with the filter paper 5A of ア De バ Application テ Star Network company test drying property, if do not carry out stronger pushing, then about 5 minutes, there be not adhering to of filter paper basically.In addition, after 1 day, only otherwise carry out strong wiping, just has good fixation performance.
In addition, part also is liquid (foaming) few image partially on the spot.This is because less except moistening dosage, is about 15 quality %, solid substance amount as many as 31 quality %.
Because the wetting agent of each printing ink of embodiment 34～36 is many, therefore to compare with each printing ink of embodiment 31～33, drying property is slower, but through after 3 days, even part on the spot, only otherwise carry out strong wiping, image just can not come off.To compare solid substance few with embodiment 31～33, the therefore relatively easy liquid (foamings) partially that produces on big part on the spot, but for non-on the spot partly small area and relate to the place of literal, during printing without any the problem of image aspect.To compare wetting agent many with embodiment 31～33, and jetting stability is good.In embodiment 31～33, place the spray nozzle clogging that produces after 1 day and can recover by cleaning, can not print according to purposes with going wrong.
As mentioned above, because the moistening dosage of these high solid substances and high resin concentration printing ink is few to 10 quality %, even so this recording medium that does not absorb water of polyester film, can have following rapid-drying properties in several minutes: even push filter paper consumingly, printing ink can not be attached on the filter paper yet yet.If moistening dosage is 10～20 quality %, then, also can obtain enough fixation performances after a few days even without heating unit is set especially.In addition, even printing back several minutes, only otherwise advance consumingly and push, printing ink often can not stick on the paper.If moistening dosage is 20～30 quality %, it is difficult then reaching the photographic fixing drying about several minutes, but through after a few days, and resin is many can the generation effect, and fixation performance is improved.In this case, for photographic fixing at short notice, heater meanses such as employing microwave oven are effective.If moistening dosage surpasses 30 quality %, if heat drying does not just have practical drying property.
In addition, these printing ink also can print non-porous base materials such as glass, metals.Particularly only during printing word, no problem fully on image.
If recording ink of the present invention prints on common paper, then can obtain high image density, back side concentration low, develop the color, do not have and ooze the image of spreading and sinking in.In addition, even for low, the level and smooth printing of water receptivity, also no problem on the rate of drying, can obtain distinctness, near the image of print, therefore applicable to ink medium group, print cartridge, ink recorded matter, ink-jet recording device and ink jet recording method.
Ink medium group of the present invention, when on the low non-porous base material of water-retaining capacities such as plastic sheets such as polyester chips, plastic layer platen, plastic coated paper, glass, metal, printing, wetting property, drying property, fixation performance are good, and by greatly reducing moistening dosage, make special devices such as need not well heater, in addition, need not use ultraviolet curing ink or oil-based ink, only use the water color ink just can be at the enterprising line item of above-mentioned plastic film.
Ink-jet recording device of the present invention and ink jet recording method for example, are specially adapted to ink-vapor recording printer, picture unit, copy device, printing/fax/duplicating compounding machine etc. applicable in the various records of taking ink-jet recording.

Claims (29)

1. recording ink comprises at least: contains tinting material and resin and is being that solid solids component, boiling point are higher and be the liquid component and the water of liquid under 25 ℃ than water under 25 ℃, wherein,
The total content of aforesaid liquid composition in above-mentioned recording ink is below the 20 quality %,
The total content of above-mentioned solids component in above-mentioned recording ink is more than the 20 quality %, and the above-mentioned relatively solids component total amount of the total content of the resinous principle in this solids component is 40～95 quality %.
2. the described recording ink of claim 1, wherein, it is resin particle below 25 ℃ that resin contains second-order transition temperature, and the volume average particle size of this resin particle is 10～1,000nm.
3. the described recording ink of claim 1, wherein, tinting material is the polymer emulsion type pigment that forms by the colorant that comprises water-insoluble or slightly water-soluble in polymer particles.
4. the described recording ink of claim 1, wherein, liquid component contains tensio-active agent, and this tensio-active agent is selected from least a in fluorine class tensio-active agent or the silicone based tensio-active agent.
5. the described recording ink of claim 1, its surface tension under 25 ℃ is below the 35mN/m.
6. ink medium group, it comprises recording ink and recording medium, wherein,
Above-mentioned recording ink comprises at least: contain tinting material and resin and be that solid solids component, boiling point are higher and be the liquid component and the water of liquid under 25 ℃ than water under 25 ℃, the total content of this liquid component in above-mentioned recording ink is below the 20 quality %;
Above-mentioned recording medium has support and is arranged at least one lip-deep coating layer of this support, and is 2～35ml/m with the fixed pure water under duration of contact 100ms of dynamic scan imbibition instrumentation to the transfer amount of above-mentioned recording medium 2, and pure water is 3～40ml/m to the transfer amount of above-mentioned recording medium under duration of contact 400ms 2
7. ink medium group, it comprises recording ink and recording medium, wherein,
Above-mentioned recording ink comprises at least: contains tinting material and resin and is being that solid solids component, boiling point are higher and be the liquid component and the water of liquid under 25 ℃ than water under 25 ℃,
The total content of aforesaid liquid composition in above-mentioned recording ink is below the 30 quality %,
The total content of above-mentioned solids component in above-mentioned recording ink is more than the 20 quality %, and the total content of the resinous principle in this solids component is 40～95 quality % with respect to above-mentioned solids component total amount;
Above-mentioned recording medium has support and is arranged at least one lip-deep coating layer of this support, and is 2～35ml/m with the fixed pure water under duration of contact 100ms of dynamic scan imbibition instrumentation to the transfer amount of above-mentioned recording medium 2, and pure water is 3～40ml/m to the transfer amount of above-mentioned recording medium under duration of contact 400ms 2
8. the described ink medium group of claim 7, wherein, it is resin particle below 25 ℃ that resin contains second-order transition temperature, and the volume average particle size of this resin particle is 10～1,000nm.
9. the described ink medium group of claim 7, wherein, tinting material is the polymer emulsion type pigment that forms by the colorant that comprises water-insoluble or slightly water-soluble in polymer particles.
10. ink medium group, it comprises recording ink and recording medium, wherein,
Above-mentioned recording ink comprises at least: contains tinting material and resin and is being that solid solids component, boiling point are higher and be the liquid component and the water of liquid under 25 ℃ than water under 25 ℃,
The total content of aforesaid liquid composition in above-mentioned recording ink is below the 30 quality %;
Above-mentioned recording medium comprises non-porous base material.
11. the described ink medium group of claim 10, wherein non-porous base material are to be selected from plastic film, plastic layer platen, plastic coated paper, glass and the metal any.
12. the described ink medium group of claim 10, wherein non-porous base material is a polyester film.
13. the described ink medium group of claim 10, wherein, it is resin particle below 25 ℃ that resin contains second-order transition temperature, and the volume average particle size of this resin particle is 10～1,000nm.
14. the described ink medium group of claim 10, wherein, tinting material is the polymer emulsion type pigment that forms by the colorant that comprises water-insoluble or slightly water-soluble in polymer particles.
15. print cartridge, it forms by recording ink is contained in the container, and described recording ink comprises at least: contain tinting material and resin and be that solid solids component, boiling point are higher and be the liquid component and the water of liquid under 25 ℃ than water under 25 ℃,
The total content of aforesaid liquid composition in above-mentioned recording ink is below the 20 quality %,
The total content of above-mentioned solids component in above-mentioned recording ink is more than the 20 quality %, and the total content of the resinous principle in this solids component is 40～95 quality % with respect to above-mentioned solids component total amount.
16. moisture retention liquid, it is to be selected from (1) to wrap that liquid medium, (3) that aqueous liquid medium, (2) are main component with water are higher than water with water and boiling point and be that the liquid component of liquid is that the liquid medium of main component comprises the composition identical with recording ink with (4) under 25 ℃, and at least a in 25 ℃ of liquid mediums that lack than this recording ink for the content of solid solids component down.
17. ink jet recording method, it comprises at least recording ink is applied stimulation, makes this recording ink flight, the printing ink of document image flight operation on recording medium, wherein,
Above-mentioned recording ink comprises at least: contains tinting material and resin and is being that solid solids component, boiling point are higher and be the liquid component and the water of liquid under 25 ℃ than water under 25 ℃,
The total content of aforesaid liquid composition in above-mentioned recording ink is below the 30 quality %,
The total content of above-mentioned solids component in above-mentioned recording ink is more than the 20 quality %, and the total content of the resinous principle in this solids component is 40～95 quality % with respect to above-mentioned solids component total amount;
Above-mentioned recording medium has support and is arranged at least one lip-deep coating layer of this support, and is 2～35ml/m with the fixed pure water under duration of contact 100ms of dynamic scan imbibition instrumentation to the transfer amount of above-mentioned recording medium 2, and pure water is 3～40ml/m to the transfer amount of above-mentioned recording medium under duration of contact 400ms 2
18. the described ink jet recording method of claim 17 wherein, behind document image on the recording medium, carries out drying by at least a operation that this image is implemented in heating and the air-supply.
19. ink jet recording method, it comprises at least recording ink is applied stimulation, makes this recording ink flight, the printing ink of document image flight operation on recording medium, wherein,
Above-mentioned recording ink comprises at least and contains tinting material and resin and be that solid solids component, boiling point are higher and be the liquid component and the water of liquid under 25 ℃ than water under 25 ℃,
The total content of aforesaid liquid composition in above-mentioned recording ink is below the 30 quality %;
Above-mentioned recording medium comprises non-porous base material.
20. the described ink jet recording method of claim 19 wherein, behind document image on the recording medium, carries out drying by at least a operation that this image is implemented in heating and the air-supply.
21. ink jet recording method wherein, when stopping ink-vapor recording for a long time, utilizes the described moisture retention liquid of claim 16 to substitute recording ink, when restarting ink-vapor recording, utilizes above-mentioned recording ink to substitute above-mentioned moisture retention liquid.
22. ink jet recording method wherein, when stopping ink-vapor recording for a long time, is supplied with the described moisture retention liquid of claim 16 in the cladding system that covers the record-header nozzle.
23. the ink medium group, it comprises recording ink and recording medium, wherein,
Above-mentioned recording ink contains at least: contain the colorant of water-insoluble or slightly water-soluble and pigment, water-dispersed resin particulate and the wetting agent of the polymer emulsion type that forms in polymer particles, the pigment of above-mentioned polymer emulsion type becomes component with the total solids of above-mentioned water-dispersed resin particulate be more than the 20 quality %, and above-mentioned wetting dosage is more than the 20 quality %; And,
The fixed pure water under duration of contact 100ms is 2～35ml/m to the transfer amount of above-mentioned recording medium to utilize dynamic scan imbibition instrumentation 2, and the pure water under duration of contact 400ms is 3～40ml/m to the transfer amount of above-mentioned recording medium 2
24. ink jet recording method, it comprises at least the recording ink in the ink medium group is applied stimulation, make this recording ink flight, the drying process that the printing ink of document image flies operation and will be recorded in the image dried on the recording medium on the recording medium in above-mentioned ink medium group, wherein
Above-mentioned ink medium group is the described ink medium group of claim 23.
25. the ink medium group, it comprises recording ink and recording medium, wherein,
Above-mentioned recording ink contains tinting material, water-dispersed resin and wetting agent at least, and the total content of the solids component in this recording ink is more than the 20 quality %, the content of above-mentioned wetting agent is more than the 20 quality %, this wetting agent is independent glycerine, perhaps the content of glycerine in above-mentioned wetting agent is more than the 80 quality %, and
The fixed pure water under duration of contact 100ms is 2～35ml/m to the transfer amount of above-mentioned recording medium to utilize dynamic scan imbibition instrumentation 2, and the pure water under duration of contact 400ms is 3～40ml/m to the transfer amount of above-mentioned recording medium 2
26. ink jet recording method, it comprises at least the recording ink in the ink medium group is applied stimulation, make this recording ink flight, the drying process that the printing ink of document image flies operation and will be recorded in the image dried on the recording medium on the recording medium in above-mentioned ink medium group, wherein
Above-mentioned ink medium group is the described ink medium group of claim 25.
27. ink recorded matter, it has the image that service recorder forms on recording medium with printing ink, wherein,
Above-mentioned recording medium has support and is arranged at least one lip-deep coating layer of this support, and is 2～35ml/m with the fixed pure water under duration of contact 100ms of dynamic scan imbibition instrumentation to the transfer amount of recording medium 2, and pure water is 3～40ml/m to the transfer amount of recording medium under duration of contact 400ms 2
Above-mentioned recording ink comprises at least: contains tinting material and resin and is being that solid solids component, boiling point are higher and be the liquid component and the water of liquid under 25 ℃ than water under 25 ℃,
The total content of aforesaid liquid composition in above-mentioned recording ink is below the 30 quality %,
The total content of above-mentioned solids component in above-mentioned recording ink is more than the 20 quality %, and the total content of the resinous principle in this solids component is 40～95 quality % with respect to above-mentioned solids component total amount.
28. ink recorded matter, it has the image that service recorder forms on recording medium with printing ink, wherein,
Above-mentioned recording medium comprises non-porous base material;
Above-mentioned recording ink comprises at least: contains tinting material and resin and is being that solid solids component, boiling point are higher and be the liquid component and the water of liquid under 25 ℃ than water under 25 ℃,
The total content of aforesaid liquid composition in above-mentioned recording ink is below the 30 quality %.
29. the described ink recorded matter of claim 28, wherein, recording medium is a polyester film.
CN 200710137903 2006-01-18 2007-01-18 Recording ink as well as ink media set, ink cartridge, ink recorded matter, inkjet recording apparatus and inkjet recording method Pending CN101096479A (en)

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