CN1933978A - Liquid composition, set of liquid composition and ink, ink-jet recording device and method for forming image - Google Patents
Liquid composition, set of liquid composition and ink, ink-jet recording device and method for forming image Download PDFInfo
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- CN1933978A CN1933978A CN 200580008373 CN200580008373A CN1933978A CN 1933978 A CN1933978 A CN 1933978A CN 200580008373 CN200580008373 CN 200580008373 CN 200580008373 A CN200580008373 A CN 200580008373A CN 1933978 A CN1933978 A CN 1933978A
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Abstract
A liquid composition for use in a method for recording an image having a step of applying an ink containing a coloring material in a dissolved state or a dispersed state on a recording medium and a step of applying, on the above recording medium, a liquid composition destabilizing the dissolved state or a dispersed state of the above coloring material in the ink by the contact with the ink, characterized in that the above liquid composition comprises a multi-valent metal ion, water and water-soluble organic compounds 1 and 2, the liquid composition contains the above water-soluble organic compound 1 in a content X(%) of 15 mass % or more, and a content X(%) of the above water-soluble organic compound in the liquid composition and a content Y(%) of the above water-soluble organic compound in the liquid composition satisfy a specific relationship.
Description
Technical field
The present invention relates to fluid composition, complete fluid composition and ink, image recording process, relate in particular to by being used in combination fluid composition and the ink fluid composition under situation about printing on the recording medium, complete described fluid composition and ink, ink-jet recording apparatus and image forming method.
Background technology
As ink jet recording method, a kind of scheme is provided, they are different with common ink jet recording method, have to be used to make the image better fluid that becomes, by make before the injection record ink aforesaid liquid attached to recording medium on the back form the method for image.For example, disclose after adhering to the liquid with alkaline polymer, record comprises the method (consulting for example Japanese kokai publication sho 63-60783 communique) of the ink of anionic property dyestuff.
But this separates out on recording medium said method by making dyestuff, though can suppress image bleeding, improve the resistance to water of image, the effect that suppresses the bleeding between the color inks of different tones is insufficient.In addition, because the dyestuff of being separated out skewness on record-paper easily, thereby the even sense of image quality reduces.Particularly use common paper as situations such as recording mediums under because to the spreadability variation of paper pulp fiber, thereby can obviously observe this tendency.
On the other hand, in using the system of pigment as the colorant of ink, in order to alleviate the bleeding in the colour print product, ink that comprises pigment dispersion and the ink set (consulting for example Japanese kokai publication hei 9-118850 communique) that comprises the ink of polyvalent metal have been proposed to be used in combination.In the case, be subjected to following restriction: as the ink that comprises polyvalent metal, must use the polyvalent metal of having considered with the compatibility of colorant, promptly to have considered the stability of ink, thereby have the problem that is difficult to obtain sufficient image color.
As solution to the problems described above, proposed after the fluid composition that will comprise polyvalent metal is applied on the recording medium in advance, printing has the ink of the character that reacts with the aforesaid liquid composition, thus the recording method (hereinafter referred to as two liquid systems) of the raising of the uniformity of realization image and image color.For example, disclose, as record-paper, use has been coated with the common paper of the solution that comprises dissociating property multivalent metal salt of ormal weight, as ink mist recording liquid, use to have specific acid number and contain the water-soluble resin and the pigment that in the presence of alkali compounds, are dissolved in the aqueous medium, have the ink jet recording method (consulting for example TOHKEMY 2000-94825 communique) that specific capillary ink prints.
On the other hand, applied the so-called curling phenomenon that also there is warpage in the recording medium of moisture or curls.As relaxing, suppress the method that this curls, several method had been proposed in the past.For example, proposed to comprise the ink for inkjet (consulting for example Japanese kokai publication hei 4-332775 communique) that has the solid matter in 4 above hydroxyls and water soluble or the water-soluble solvent in the molecular structure.In addition, proposed to comprise carbohydrate, glycitols, specific amide compound ink (consulting for example Japanese kokai publication hei 6-157955 communique, Japanese kokai publication hei 6-240189 communique, Japanese kokai publication hei 9-16539 communique, Japanese kokai publication hei 9-176538 communique) as anti-roll herbal leaven.In addition, propose combination and contained specific polyalcohol and the ink of glycerine (consulting for example Japanese kokai publication hei 10-130550 communique).In addition, proposed to comprise the ink (consulting for example TOHKEMY 2000-19826 number) of solvent, polymer binder, mordant, water-soluble anti-curl compound, water-soluble destarch compound, light resistance compound, defoamer etc.
Summary of the invention
The inventor obtains image to the bleeding excellence between the color inks of the inhibition of image bleeding, different tones in order to use two liquid systems, has carried out detailed research.
The method that the fluid composition that uses in two liquid systems is applied on the recording medium comprises several different methods.Can list, for example the same method of using ink-jet method with ink, and then can also list rolling method, rod is coated with method, spraying process etc.In addition, the method as fluid composition and ink being applied on the recording medium comprises following method.
(1) fluid composition is coated on method on whole of recording medium.
(2) make image forming area that fluid composition optionally only adheres to attached to ink and near the method the image forming area.
(3) method that is coated with of the mode that on recording medium, is in contact with one another of fluid composition and ink with the state of liquid.
(4) with fluid composition to the recording medium set after, that is, after the drop of fluid composition is absorbed into recording medium inside fully, apply the method for ink.
The inventor is at found that these various coating processes are studied, after on fluid composition being coated on whole of recording medium, after described fluid composition is to described recording medium set, apply the method for ink, picture characteristics the bests such as the density unevenness of gained image is even, anchorage.
But find, but produced new problem by using said method.That is, owing to coating liquid composition on whole of recording medium, recording medium bending, the phenomenon (phenomenon of curling) of curling are compared with the situation of using additive method, show more significantly.Especially, fluid composition is being applied on the recording medium, then recording medium is being transported in the tape deck, applying then in the system of this ink, recording medium takes place to curl in the carrying apply ink on the recording medium that has been coated with fluid composition till, causes that carrying is not good.Therefore, became a very big problem than further suppress to curl in the past.
Therefore, the object of the present invention is to provide a kind of jetting stability that can guarantee after the desired injector head of existing fluid composition is placed, can guarantee can not produce the disorder of the printing the beginning part when beginning to print, the jetting stability of problem such as fuzzy, the described fluid composition that the fluid composition that can relax, suppress simultaneously to curl, complete described fluid composition and ink, use are complete and the ink-jet recording apparatus and the image forming method of ink.
Above-mentioned purpose realizes by following the present invention.Promptly, fluid composition of the present invention is a kind of fluid composition that is used for image recording process, this image recording process possesses: apply with dissolved state on recording medium or comprise the operation of the ink of colorant with dispersity, and the operation that described recording medium is applied fluid composition, this fluid composition is by contacting dissolved state or the dispersity instabilityization that makes the colorant in the described ink with ink, it is characterized in that: described fluid composition comprises polyvalent metal ion at least, water, water-soluble organic compounds 1 and water-soluble organic compounds 2, and, the content X (quality %) of described water-soluble organic compounds 1 is more than the 15 quality % with respect to the fluid composition total amount, and described water-soluble organic compounds 1 satisfies following relational expression with respect to the content X (quality %) of fluid composition total amount and described water-soluble organic compounds 2 with respect to the content Y (quality %) of fluid composition total amount:
0＜Y/X≤0.9
Water-soluble organic compounds 1 be a kind of under the environment of 23 ℃ of temperature, humidity 45% water holding capacity and the difference of the water holding capacity under the environment of 30 ℃ of temperature, humidity 80% be water-soluble organic compounds below 36%, that have water-retaining property.
Water-soluble organic compounds 2 is a kind of water-soluble organic compounds except that colorant and water-soluble organic compounds 1.
In addition, complete fluid composition and ink of the present invention is characterised in that: it is the fluid composition and the ink of complete above-mentioned record.
In addition, in above-mentioned complete fluid composition and ink, described fluid composition and ink can more effectively prevent to write down curling of thing by satisfying following condition.
(condition)
5 times of dilute aqueous solution 0.3g of 800 times of dilute aqueous solution 50g of described fluid composition, described ink are mixed, after the filter filtration with 0.2 μ m after 15 minutes, maximum absorption wavelength at visible region (is using under the situation of carbon black as pigment, wavelength is 550nm) under absorbance be designated as (A), when the absorbance of mixed solution under the maximum absorption wavelength of visible region of 5 times of dilute aqueous solution 0.3g of described water-base ink and pure water 50g is designated as (B), (A) with (B) satisfy following relational expression:
(A)/(B)＜0.85。
In addition, ink-jet recording apparatus of the present invention is characterised in that: it is equipped with the fluid composition and the ink of above-mentioned record.
In addition, image forming method of the present invention is the image recording process that comprises following operation: apply the operation that comprises the ink of colorant with dissolved state or dispersity on recording medium, and, described recording medium is applied the operation of fluid composition, this fluid composition is characterized in that by contact dissolved state or the dispersity instabilityization that makes the colorant in the described ink with ink:
Described fluid composition comprises polyvalent metal ion, water, water-soluble organic compounds 1 and water-soluble organic compounds 2 at least, and, the content X (quality %) of described water-soluble organic compounds 1 is more than the 15 quality % with respect to the fluid composition total amount, and described water-soluble organic compounds 1 satisfies following relational expression with respect to the content X (quality %) of fluid composition total amount and described water-soluble organic compounds 2 with respect to the content Y (quality %) of fluid composition total amount:
0＜Y/X≤0.9
Water-soluble organic compounds 1 be a kind of under the environment of 23 ℃ of temperature, humidity 45% water holding capacity and the difference of the water holding capacity under the environment of 30 ℃ of temperature, humidity 80% be water-soluble organic compounds below 36%, that have water-retaining property.
Water-soluble organic compounds 2 is a kind of water-soluble organic compounds except that colorant and water-soluble organic compounds 1.
Under the situation of using fluid composition of the present invention as the fluid composition that is applicable to two liquid systems, can guarantee the jetting stability after injector head is placed, and the jetting stability of problems such as the printing the beginning part when guaranteeing to begin to print gets muddled, blurs, the curling of recording medium that can suppress simultaneously to be coated with fluid composition.Therefore, promptly be used in fluid composition is applied on the recording medium after recording medium be moved in the system that applies ink in the tape deck, then, it is bad also can to eliminate the carrying that curling of recording medium caused.And then, on the recording medium that has been coated with fluid composition, apply ink and the curling phenomenon of the image that obtains also can obtain more effective inhibition.
The simple declaration of accompanying drawing
Fig. 1 is the summary side sectional view of an example of ink-jet recording apparatus.
Fig. 2 is the front section view that is arranged on the fluid composition surplus display part in the ink-jet recording apparatus of Fig. 1.
Fig. 3 is the summary side sectional view to the additional state of the fluid composition of the ink-jet recording apparatus of Fig. 1.
Fig. 4 is the approximate three-dimensional map of an example of ink-jet recording apparatus.
Fig. 5 is the longitudinal section cutaway view of an example of print cartridge.
Fig. 6 is installed in general view under the state on the record head for print cartridge.
Fig. 7 is the schematic diagram of the measurement result (it is poor that environment causes) of the water holding capacity of water-soluble organic compounds.
Fig. 8 is the schematic diagram of difference of the water holding capacity of water-soluble organic compounds.
The specific embodiment
Below, preferred embodiment the present invention will be described in more detail by enumerating.
[water-soluble organic compounds] with water-retaining property
Curling after being applied to moisture liquid medium on the recording medium, can think and have certain relation with the evaporation that is applied to the moisture on the recording medium, therefore, the inventor in ink for inkjet and the coating fluid the water holding capacity of normally used water-soluble organic compounds carried out following studying in great detail.
At first, prepare the aqueous solution of 20 quality % of various water-soluble organic compounds, each accurate weighing 10g puts into glass dish, is placed in the environment of 23 ℃ of temperature, humidity 45%.In addition, place the pure water that does not contain water-soluble organic compounds simultaneously too.Along with the evaporation of moisture, the solution amount in the glass dish reduces, and quality reaches certain subsequently.The glass dish that pure water only the is housed pure water at this moment of Fang Zhiing all evaporates simultaneously, thereby the material that remains in the glass dish that comprises water-soluble organic compounds can be thought the moisture that water-soluble organic compounds and this material are kept, by following formula, calculate the water holding capacity of each compound.
Then, above-mentioned glass dish is transferred in the environment of 30 ℃ of temperature, humidity 80%, same wait is measured the residual weight under this environment, and is obtained water holding capacity according to following formula to reaching balance.And then, same glass dish is transferred to once more in the environment of 23 ℃ of temperature, humidity 45%, measure residual weight, similarly obtain water holding capacity.Resulting result as shown in Figure 7.In addition, the difference of the water holding capacity under two kinds of environment as shown in Figure 8.
The inventor thinks, the certain relation of curling existence that difference and common paper took place of the water holding capacity under the above-mentioned environment.Therefore, the aqueous solution that will comprise the water-soluble organic compounds of above-mentioned research is coated on the common paper, check the generation of curling, found that, the difference of the water holding capacity under the environment of 23 ℃ of temperature, temperature 45% and water holding capacity under the environment of 30 ℃ of temperature, humidity 80% be water-soluble organic compounds 1 36% below significantly suppress curling.Therefore, further preparation only comprises the ink of colorant and additive and these water-soluble organic compounds, observes the generation of curling.Found that,, also take place to curl even after printing, place after a couple of days at normal temperatures.
But, the fluid composition of only being made up of water-soluble organic compounds 1 is installed to from the ink jet print head of jet droplets, and carrying under this state under the situation of also placing for a long time on the ink-jet recording apparatus, the jetting stability variation that produce because spray nozzle clogging etc. causes, the new problems such as disorder of the printing the beginning part when under low temperature, low wet environment, beginning to print.
Therefore, the inventor etc. guarantee and the jetting stability of existing fluid composition par for when curl control is more than to a certain degree, have carried out further research.Consequently, in fluid composition, except water-soluble organic compounds 1, also comprise polyvalent metal and other water-soluble organic compounds except that water-soluble organic compounds 1, more particularly, the difference of the water holding capacity under the environment of 30 ℃ of water holding capacity under the environment of 23 ℃ of temperature, humidity 45% and temperature, humidity 80% is greater than 36% water-soluble organic compounds 2, and comprises with the ratio that satisfies following condition, just can address the above problem.
0＜Y/X≤0.9
(X: with respect to content (quality %), the Y of the water soluble compound 1 of fluid composition total amount :) with respect to the content (quality %) of the water soluble compound 2 of fluid composition total amount
In addition, research according to the inventor, want more effectively to have suppressed to be coated with the curling phenomenon of the recording medium of fluid composition, except above-mentioned condition, must be controlled at the content X (quality %) of water-soluble organic compounds 1 with respect to the fluid composition total amount be more than 15%.
In the present invention, with water-soluble organic compounds 1 with respect to the content X (quality %) of the total amount of fluid composition be controlled to be more than 15% the reasons are as follows described.Even above-mentioned water-soluble organic compounds 1 is below 15% with respect to the total amount of fluid composition, also can suppress curling to a certain extent under to the profuse situation of the applied amount of recording medium at fluid composition.But under the situation of the anchorage of considering to have applied the print position behind the ink etc., it is the least possible to the coating weight of recording medium that employed fluid composition requires fluid composition in two liquid systems.Like this fluid composition to the few situation of the applied amount of recording medium under, specifically, in order to be 3.0g/m in applied amount
2Also suppress the phenomenon of curling in the following situation, just the content X (quality %) of water-soluble organic compounds 1 with respect to the fluid composition total amount must be controlled at more than the 15 quality % at least.
In addition, the total content X+Y (quality %) of water-soluble organic compounds 1 and water-soluble organic compounds 2 is more than the 30 quality % with respect to the total amount of fluid composition preferably.In addition, consider that from the crimp property aspect content of preferred water is below the 76 quality % with respect to the fluid composition total amount, more preferably below the 71 quality %.
And then more preferably water-soluble organic compounds 2 is Y＜15 quality % with respect to the content Y (quality %) of the total amount of fluid composition, and above-mentioned water-soluble organic compounds 1 is selected from polyalcohol and amide compound.Especially preferred is that water-soluble organic compounds 1 is the polyalcohol with amido link, and the molecular weight Mw of water-soluble organic compounds 1 is positioned at the scope of 100≤Mw≤1000.
In addition, the inventor uses water-soluble organic compounds 1 and 2 to carry out found that of various researchs, according to the coating weight of fluid composition on recording medium, the difference of content of water in the fluid composition,, can suppress curling by optionally using water-soluble organic compounds 1.That is be 10.0g/m to the coating weight of recording medium, at fluid composition
2More than and the content X (quality %) of water-soluble organic compounds 1 with respect under the situation of fluid composition total amount less than 25 quality %, perhaps, be 10.0g/m to the coating weight of recording medium at fluid composition
2More than and the content of water with respect under the situation of fluid composition total amount greater than 71 quality %, preferably comprise the following water-soluble organic compounds 1-1 that curls that can the long term inhibition printed product and can be suppressed at and print these the two kinds of compounds of following water soluble compound 1-2 that curl that produce in the short period of back.Particularly under these conditions, at the fluid composition that comprises water-soluble organic compounds 1-2 with do not contain in the fluid composition of water-soluble organic compounds 1-2, print the significant difference of the curling phenomenon that is produced in the short period of back.
Water-soluble organic compounds 1-1:
Molecular weight Mw is positioned at the scope of 100≤Mw≤1000, and
(A) have the polyalcohol of at least 3 above ehter bonds, perhaps have the polyalcohol of 3 above OH bases, perhaps except OH base, ehter bond group, have the polyalcohol of at least 1 above hydrophily conjugated group (conjugated group) with hydrogen associativity; And
(B) water-soluble amide compound.
Water-soluble organic compounds 1-2:
Molecular weight Mw is positioned at the scope of 100≤Mw≤150, and has the alkane glycol of OH base at two ends of main chain.
Fluid composition by using above-mentioned composition can be guaranteed as the desired jetting stability of fluid composition as employed fluid composition in two liquid systems, also can alleviate, suppress simultaneously curling.
On the other hand, the method that fluid composition is coated on the recording medium is not an ink jet recording method, but be applied to by rolling method under the situation of the method on the recording medium, produce following new problem: be difficult to suppress the water evaporates of fluid composition on surface of applicator roll etc., the solid constituent in the fluid composition is separated out on surface of roller etc. and image is exerted an influence.Therefore, the inventor finds, even as under situation about by rolling method etc. fluid composition being applied on the recording medium, also suppressing curling, and then preventing the method for the problem of solid constituent of separating out on the roller surface etc. that occurs as new problem, in preferred water soluble organic compound 1 and the water-soluble organic compounds 2 at least a kind uses is that the environment of 25 ℃ of temperature, humidity 40% is the compound of liquid down.In addition, because at least a kind in water-soluble organic compounds 1 and the water-soluble organic compounds 2 is to be the compound of liquid down at normal temperature (25 ℃), so the jetting stability after the ink gun placement also becomes better.
[fluid composition]
Be described in detail at the composition, the rerum natura that constitute fluid composition of the present invention, coating process and the coating weight that is applied on the recording medium below.
(water-soluble organic compounds) with water-retaining property
Water-soluble organic compounds 1
Water-soluble organic compounds 1 of the present invention be a kind of under the environment of 23 ℃ of temperature, humidity 45% water holding capacity and the difference of the water holding capacity under the environment of 30 ℃ of temperature, humidity 80% be water-soluble organic compounds below 36%, that have water-retaining property.In addition, from curl characteristics, water-soluble organic compounds 1 can be divided into water-soluble organic compounds 1-1 and water-soluble organic compounds 1-2.More particularly, can list compound as follows.In addition, the water-soluble organic compounds that what is called of the present invention has a water-retaining property is the definition according to above-mentioned water holding capacity specifically, and the water holding capacity under the environment of 23 ℃ of temperature, humidity 45% is the water-soluble organic compounds of the water more than 5%.
Water-soluble organic compounds 1-1
Mean molecule quantity is 200 (principal component is a TEG), 300 (principal component is six ethylene glycol), 400 (principal component is nine ethylene glycol), 600 (principal component is ten triethylene glycols), 1000 polyethylene glycol such as (principal component are 20 diethylene glycols), 1,2, the 6-hexanetriol, trimethylolpropane, trimethylolethane, pentaerythrite, 3 yuan of diglycerols etc. or more polynary polyalcohol, glucose, D-sorbite, the double hydroxyethyl sulfone, N, N-pair-(2-ethoxy)-urea, four-(2-ethoxy)-benzene diamides etc. has carbonyl, sulfuryl, amide groups etc. have the polyol compound of the group of hydrogen associativity.Wherein, preferred especially mean molecule quantity is 200 (principal component is a TEG), 300 (principal component is six ethylene glycol), 400 (principal component is nine ethylene glycol), 600 (principal component is ten triethylene glycols), 1000 polyethylene glycol such as (principal component are 20 diethylene glycols), 1,2,6-hexanetriol, trimethylolpropane, double hydroxyethyl sulfone, N, N-is two-(2-ethoxy)-urea, and N more preferably, N-is two-(2-ethoxy)-urea.
Water-soluble organic compounds 1-2
1,5-pentanediol, 1,6-hexylene glycol, 1,7-heptandiol, 3-methyl isophthalic acid, 5-pentanediol, 2-amino-2-methyl-1, ammediol, 2-amino-2-ethyl-1, ammediol etc. can have substituent two ends at carbon backbone chain and have-the alkane glycol of OH base.Wherein, preferred especially 1,5-pentanediol, 1,6-hexylene glycol.
Water-soluble organic compounds 2
Water-soluble organic compounds 2 among the present invention is a kind of water-soluble organic compounds except that colorant and water-soluble organic compounds 1, that is, the difference of the water holding capacity under the environment of the water holding capacity under the environment of 23 ℃ of temperature, humidity 45% and 30 ℃ of temperature, humidity 80% is greater than 36% and do not satisfy the water-soluble organic compounds of the regulation of water-soluble organic compounds 1.In addition, water-soluble colorant etc. is not comprised in the water-soluble organic compounds 2 of the present invention.More particularly, can list following compound.Can list the alkylene glycol class that alkylidenes such as ethylene glycol, propane diols, diethylene glycol, triethylene glycol, hexylene glycol comprise 2～6 carbon atoms; Glycerine; 2-Pyrrolidone; Urea and ethylidene-urea etc. have the water soluble compound of the few hydrophilic radical of carbon number.Wherein, preferred especially diethylene glycol, glycerine, 2-Pyrrolidone, urea, ethylidene-urea.
Compound such as urea, ethylidene-urea is because molecular weight is little, even addition is big, viscosity also is difficult to rise, so preferred.Be used in combination by compounds such as urea, ethylidene-urea are further demonstrated water miscible compound with water-miscible organic solvent or dyestuff etc., can be used as the compound with water-retaining property of the present invention.In addition, the measurement result of the water holding capacity of the ethylidene-urea of Fig. 7 (it is poor that environment causes) is to use data when testing with dyestuff.
In addition, in the present invention, water-soluble organic compounds 1 that is used in combination and water-soluble organic compounds 2 one of at least preferably be liquid down at normal temperature (25 ℃).This is in the method for using ink-jetting style or use method that a plurality of rollers shift as fluid composition of the present invention is coated under the situation of the method on the recording medium, prevents to be accompanied by the evaporation of fluid composition and set between ink gun part or the roller occurs.
(polyvalent metal ion and salt thereof)
The polyvalent metal ion that can preferably use in fluid composition of the present invention specifically can list for example Ca
2+, Cu
2+, Ni
2+, Mg
2+, Zn
2+, Sr
2+And Ba
2+Deng bivalent metal ion, Al
3+, Fe
3+, Cr
3+And Y
3+Deng trivalent metal ion, but be not limited to these ions.In order in fluid composition, to comprise these polyvalent metal ions, use the salt of polyvalent metal.Salt is meant above-mentioned polyvalent metal ion of enumerating and the slaine that can form with the anion of these ions binding, but essential water soluble.Be used to form the suitable anion of salt, from solubility, can enumerate the conjugate base of strong acid, for example the conjugate base NO of strong acid nitric acid, sulfuric acid, hydrochloric acid
3 -, SO
4 2-, Cl
-, NO particularly
3 -Solubility to water is good, so preferred.
In addition, this has wherein known that the strong acid salt of the metal ion that the ability that comprises the composition instabilityization that makes in the ink is high has the tendency that the easier pH of causing reduces.The inventor uses the carbon black dispersion aqueous solution (dispersant: styrene-propene acid, acid number 200, the quality %=0.2 of the quality % of dispersant/pigment) of 4 quality %, in the situation of studying with the nitrate of various polyvalent metal ions, according to Fe
3+, Y
3+, Al
3+＞Cu
2+, Ca
2+＞Mg
2+, Sr
2+Order, the ability height of instabilityization, and cause the reduction of pH according to this order easily.Under the situation of the salt that uses these polyvalent metal ions and strong acid to form, from reactive aspect of ink, be present in the concentration of metal ions in the fluid composition, preferably add Fe
3+, Al
3+And Y
3+Be more than the 0.2 quality %, Ca
2+And Cu
2+Be more than the 0.5 quality %, Mg
2+And Sr
2+Be more than the 1.0 quality %.
In addition, at the Mg lower with the ability that makes the ink instabilityization
2+, Sr
2+In the salt that forms, if wish also to obtain the Fe higher with ability
3+, Al
3+And Y
3+Salt has equal ability, then causes the pH reduction in time of fluid composition easily.
In addition, in the present invention, from viewpoints such as easiness reactive and coloring and operation, polyvalent metal ion is preferably Ca
2+, Mg
2+, Sr
2+, Al
3+And Y
3+, Ca more preferably
2+
With respect to the total amount of fluid composition, the content of the polyvalent metal ion in the fluid composition is preferably 0.01 quality %～10 quality %.1.0 quality %～5 quality % more preferably, and then, preferably comprise the polyvalent metal ion of 2.0 quality %～4.0 quality % with respect to fluid composition in order to give full play to the function that makes the ink instabilityization, to obtain high-caliber image uniformity, optical concentration.In addition, also can in fluid composition, comprise the polyvalent metal ion that surpasses 10 quality %.But, even add, can not expect to make the function of ink instabilityization to enlarge markedly more than 10 quality %, for these reasons, needn't excessively comprise usually.
(reason of the variation that causes owing to preservation)
Comprise in fluid composition under the situation of polyvalent metal ion, have following situation: fluid composition changes owing to preserving, and can not obtain high optical concentration, and the initial stage is different with resulting image quality after after a while.The cause inferred that causes above-mentioned phenomenon is as follows.
Because acidic group such as the oxidized for example carboxyl that produces of organic compound of fluid composition and polyvalent metal ion react, the counter ion counterionsl gegenions of polyvalent metal ion (anion of polyvalent metal) generate acid with the proton of above-mentioned acidic group, and the pH value of fluid composition reduces.If the pH value of fluid composition changes, then the reactivity of fluid composition also changes, thereby resulting image quality also changes.For example, if the reactivity of fluid composition reduces, then colorant is impregnated in the recording medium, thereby can not obtain high optical concentration, and colorant reaches near recording medium rear side (print through of so-called colorant).
Therefore, the inventor finds, in fluid composition, comprise under the situation of polyvalent metal ion, by conjugate base that comprises strong acid simultaneously and the conjugate base that hydrogen ion concentration is changed weak acid with cushioning effect, can give cushioning effect to fluid composition, and the reduction of pH value as described above is suppressed to Min..In addition, the pH value among the present invention is the value of measuring by conventional method under 25 ℃.
The pH value of fluid composition of the present invention is preferably more than 2.If the pH value is less than 2, then parts surfaces such as China ink jar or roller are corroded in the one-tenth branch in the fluid composition, and the constituent of parts is dissolved in the fluid composition, and image is produced harmful effect, so not preferred.Preferably the pH value with fluid composition is controlled at 2～7, more preferably in 3～6 the scope.If in this scope, owing to polyvalent metal ion more stably is present in the fluid composition, thereby can fully guarantees the reactivity of fluid composition, in addition, can fully obtain following cushioning effect, thereby also can keep the long-time stability of fluid composition.
(to the cushioning effect of hydrogen ion concentration variation)
" relax hydrogen ion concentration change effect " of the present invention be meant, when adding 0.1N aqueous solution of nitric acid 1.0ml with respect to the fluid composition of 50ml, add before the aqueous solution of nitric acid with add hydrogen ion concentration after the aqueous solution of nitric acid be changed to 1 * 10
-4Below (following table is shown " cushioning effect ").The variation of hydrogen ion concentration can come out from the change calculations of pH value (following table is shown " variation of hydrogen ion concentration ").PH value after initial pH value is designated as a, interpolation aqueous solution of nitric acid becomes under the situation of b, can calculate hydrogen ion concentration by following formula.
The variation of hydrogen ion concentration (mol/L)=(10
-b)-(10
-a)
In the present invention, in order to obtain cushioning effect, preferably in fluid composition, comprise buffer.The preferred examples of buffer can be used acetate such as sodium acetate, potassium acetate, lithium acetate, hydrophosphate, bicarbonate, perhaps polybasic carboxylic acid hydrogen salts such as hydrogen phthalate sodium, Potassium Hydrogen Phthalate.In addition, the instantiation of polybasic carboxylic acid can also list malonic acid, maleic acid, butanedioic acid, fumaric acid, itaconic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), adipic acid, decanedioic acid, dimeric dibasic acid, PMA, trimellitic acid etc. except phthalic acid.In addition, if the pH value of fluid composition can be remained on material in the preferred range by adding this material, the existing known compound that the pH value is had a cushioning effect all can be used for the present invention.But, in the present invention, from as with the suitable pH value of the pH value of the composition of ink and usefulness under demonstrate cushioning effect aspect, especially preferably use acetate as buffer.
In addition, in addition, when in ink, comprising buffer in order to obtain cushioning effect, the instabilityization that helps the colorant of ink from the metal ion of buffer, thereby state in the use under the situation of fluid composition, can obtain using the fluid composition that only has polyvalent metal ion the high optical concentration that can't obtain.If in image forms, use fluid composition of the present invention, the above-mentioned functions that obtains by the aforesaid liquid composition acts synergistically, not only can further suppress curling of printed product, and from use initial stage of fluid composition to the image that after after a while, can stably obtain demonstrating very high optical concentration.
(rerum natura)
The inventor finds that the colorant aggregation in the recording medium exists many more in surface layer part, and then the amount of crimp of the record thing that obtains by two liquid systems can be relaxed more.
As aggregation is present in from the condition of recording medium superficial layer part to the position that depth direction permeates a little, can list the reactivity of control fluid composition and ink.In addition, have in a large number from recording medium superficial layer part to about 30 μ m with interior that to be used to make the polyvalent metal ion of the abundant amount that colorant assembles be very important.Can think, the polyvalent metal ion that comprises in order to make in the fluid composition exists with interior to about 30 μ m in a large number from recording medium superficial layer part, the amount of the polyvalent metal ion that is comprised in the fluid composition obviously has much relations, in addition, fluid composition also has much relations to the impregnability and the coating weight of recording medium.
Fluid composition is with when recording medium contacts, and permeates along the fiber of recording medium owing to be subjected to the influence of solvent or surfactant etc.In addition, can think: in the time of with this infiltration, the liquid start vaporizer that is permeated, a part of losing solvent polyvalent metal begins to separate out.That is, owing to improve the reactivity of fluid composition with a spot of coating weight, so promoted infiltration and the evaporation of liquid to recording medium.The result is that a large amount of polyvalent metal ions may be stayed the position that partly is penetrated into dark slightly direction from the recording medium superficial layer.
As from the foregoing, in order to ensure the fluid composition of the present invention that comprises polyvalent metal ion common paper is had more effective dipping, the Ka value of trying to achieve by the Bristow method is preferably 1.3mLm
-2Msec
-1/2More than, coating weight is preferably 0.5g/m
2～5g/m
2, more preferably the Ka value is 3.0mLm
-2Msec
-1/2More than, coating weight is preferably 2.0g/m
2～3.0g/m
2
(other compositions)
In fluid composition, in order to obtain having the fluid composition of desirable physics value, can in the scope of not damaging target effect of the present invention, suitably add surfactant, defoamer, mould inhibitor etc., and obtain to add the effect that these brought.
(recording method, device)
Fluid composition is applied to method on the recording medium can be listed the method for using ink-jet recording and by roller etc. fluid composition is coated on method on the recording medium etc.
[ink]
Be described in detail at the composition that constitutes ink of the present invention.
(composition)
Ink of the present invention can form high quality images by using with the aforesaid liquid combination of compositions.This ink preferably in aqueous medium colorant disperse by ionic group or dissolving.
(colorant)
Employed colorant can list for example pigment such as carbon black or organic pigment in the ink of the present invention.Pigment can use a kind or be used in combination more than 2 kinds.In addition, the form of pigment can be used with the pigment of dispersant dispersion, from dispersed color, toner/microcapsules etc.Below, describe in detail at this point.
Carbon black
The instantiation of carbon black can use furnace black, dim, acetylene black, charcoal blacks such as channel black, for example Raven 7000, Raven 5750, Raven 5250, Raven5000, Raven 3500, Raven 2000, Raven 1500, Raven 1250, Raven 1200, Raven 1190 ULTRA-II, Raven 1170, Raven 1255 (above) by the manufacturing of Columbia company, Black Pearls L, Regal 400R, Regal 300R, Regal 660R, Mogul L, Monarch 700, Monarch800, Monarch 880, Monarch 900, Monarch 1000, Monarch1100, Monarch 1300, Monarch 1400, Valcan XC-72R (above) by the manufacturing of Cabot company, Color Black FW1, Color Black FW2, ColorBlack FW2V, Color Black FW18, Color Black FW200, ColorBlack S150, Color Black S160, Color Black S170, Printex 35, Printex U, Printex V, Printex 140U, Printex 140V, SpecialBlack 6, Special Black 5, Special Black 4A, Special Black 4 (above) by the manufacturing of デ グ Star サ company, No.25, No.33, No.40, No.47, No.52, No.900, No.2300, MCF-88, MA600, MA7, MA8, MA100 (above) etc. by Mitsubishi Chemical Ind's manufacturing.Certainly, be not limited to these, can use existing known carbon black.In addition, also can use magnetic particulate such as magnet, ferrite or titanium black etc. as black pigment.
Organic pigment
The instantiation of organic pigment can list toluidine red, everbright fast maroon, hansa yellow, benzidine yellow, insoluble azo colours such as pyrazolone red, lithol red, He Liao is purplish red, lithol fast scarlet nrh, solubility AZOpigments such as permanent red 2B, alizarin, indanthrene, the derivative that thioindigoid maroons etc. are obtained by vat dyestuffs, phthalocyanine blue, phthualocyanine pigments such as phthalocyanine green, quinacridone is red, quinacridone pigments such as quinacridone magenta, pyrene is red, the scarlet pyrene series pigments that waits of pyrene, the isoindolinone Huang, isoindolinone pigments such as isoindolinone orange, the benzimidazolone Huang, the benzimidazolone orange, the red benzimidazolone series pigments that waits of benzimidazolone, pyranthrone is red, pyranthrone series pigments such as pyranthrone orange, the thioindigo series pigments, the condensation azo pigment, the thioindigo series pigments, the flavanthrene Huang, amido yellow, quinoline a word used for translation ketone Huang, the nickel azophosphine, copper azomethine Huang, the perilla ketone orange, the anthrone orange, other pigment such as the red dioxazine violet of DIANTHRAQUINONE.
In addition, if, can list following pigment with Colour Index (C.I.) number expression organic pigment.Certainly, also can be to use existing known organic pigment except that following pigment.
C.I. pigment yellow: 12,13,14,17,20,24,74,83,86,93,109,110,117,120,125,128,137,138,147,148,151,153,154,166,168
C.I. pigment orange: 16,36,43,51,55,59,61
C.I. paratonere: 9,48,49,52,53,57,97,122,123,149,168,175,176,177,180,192,215,216,217,220,223,224,226,227,228,238,240
C.I. pigment violet: 19,23,29,30,37,40,50
C.I. alizarol saphirol: 15,15:1,15:3,15:4,15:6,22,60,64
C.I. naphthol green: 7,36
C.I. bistre: 23,25,26
Dispersant
State in the use under the situation of carbon black, organic pigment, preferably be used in combination with dispersant.Dispersant is fit to use and can utilizes the effect of anionic group to make above-mentioned pigment stably be dispersed in dispersant in the aqueous medium.The instantiation of dispersant comprises for example styrene-propene acid copolymer, styrene-propene acid-alkyl acrylate copolymer, styrene-maleic acid copolymer, styrene-maleic acid-alkyl acrylate copolymer, styrene-methacrylic acid copolymer, styrene-methacrylic acid-alkyl acrylate copolymer, styrene-maleic acid half ester copolymer, vinyl naphthalene-acrylic copolymer, vinyl naphthalene-maleic acid, phenylethylene-maleic anhydride-maleic acid half ester copolymer or their salt.In addition, the weight average molecular weight of these dispersants is preferably 1000～30000, is preferably 3000～15000 especially.
Self-dispersion type pigment
As colorant, can use and just can be dispersed in pigment in the aqueous medium, promptly so-called self-dispersion type pigment by need not dispersant at surface of pigments coupled ion group (anionic property group).Such pigment for example can be enumerated the self-dispersion type carbon black.The self-dispersion type carbon black can list the anionic property carbon black that is combined with the anionic property group at carbon blacksurface.
The anionic property carbon black
The anionic property carbon black can list carbon blacksurface combine at least a for example being selected from-COOM ,-SO
3M ,-PO
3HM ,-PO
3M
2In the material of anionic property group.In following formula, M represents hydrogen atom, alkali metal, ammonium or organic ammonium.Wherein, particularly by carbon blacksurface combination-COOM or-SO
3M makes dispersed good in ink of carbon black that its charged one-tenth has an anionic property, so be particularly suitable for the present invention.
Wherein, in the group with " M " expression in the above-mentioned hydrophilic radical, alkali-metal instantiation can list for example Li, Na, K, Rb and Cs etc., in addition, the instantiation of organic ammonium can list for example ammonium methyl, Dimethyl Ammonium, trimethyl ammonium, ethyl ammonium, diethyl ammonium, triethyl ammonium, methanol ammonium hydroxide, dimethanol ammonium, three methanol ammonium hydroxides etc.
And the ink of the present invention that comprises M and be the self-dispersion type carbon black of ammonium or organic ammonium can further improve the resistance to water of document image, considers from this point, is particularly suitable for using.If this can think this ink is applied on the recording medium, ammonium will decompose, and the ammonia influence of evaporation is caused.Wherein, at M is in the self-dispersion type carbon black of ammonium, can list is alkali-metal self-dispersion type carbon black at M for example, use ion-exchange with M be replaced to ammonium substitution technique, form and add the method etc. that ammonium hydroxide becomes M ammonium after the H type by adding acid.
The manufacture method of anionic property carbon black for example comprises by clorox carries out the method for oxidation processes to carbon black, can be with-COONa group chemical bond to carbon blacksurface by this method.
Wherein, above-mentioned various hydrophilic radical can directly be combined on the surface of carbon black.Perhaps, also can between carbon blacksurface and above-mentioned hydrophilic radical, insert other atomic group, make that above-mentioned hydrophilic radical and carbon blacksurface are indirect to be combined.Wherein, can to list carbon number for example be 1～12 the straight chain shape or alkylidene, replacement or unsubstituted phenylene, replacement or the unsubstituted naphthylene of a chain to the instantiation of other atomic group.Wherein, can to list carbon number for example be 1～6 the straight chain shape or the alkyl of a chain to the substituting group of phenylene and naphthylene.In addition, the example of the combination of other atomic group and hydrophilic radical for example can list-C
2H
4COOM ,-Ph-SO
3M ,-(wherein, Ph represent phenylene) such as Ph-COOM.
In the present invention, can suitably selecting then in above-mentioned self-dispersion type carbon black, two or more are used as the colorant of ink.In addition, the addition of the self-dispersion type carbon black in the ink is preferably 0.1 quality %～15 quality % with respect to the ink total amount, is preferably 1 quality %～10 quality % especially.By being set in this scope, the self-dispersion type carbon black can keep sufficient dispersity in ink.In addition, for tone of adjusting ink etc., except the self-dispersion type carbon black, can also add dyestuff as colorant.
Toner/microencapsulation pigment
As colorant, except above-mentioned material, can also use with the pigment of microencapsulations such as polymer or with the toner made around the colorant covering resin particle etc.Microcapsules originally have the dispersiveness to aqueous medium, and in order to improve dispersion stabilization, above-mentioned dispersant can further coexist in ink.In addition, using under the situation of toner as colorant, preferably use above-mentioned anionic species dispersant.
(aqueous medium)
, just have no particular limits so long as can be used for the aqueous medium of ink in order to the aqueous medium of dispersion color.In addition, when on recording medium, applying ink, preferably be adjusted to viscosity and surface tension by ink-jet method (for example Bubble Jet (registration mark) method etc.) with ink-jet spray characteristic.
Employed aqueous medium can list the mixed solvent of water for example or water and water miscible organic solvent in the ink of the present invention.Water-miscible organic solvent especially preferably has the effect of the ink dried of preventing.Specifically, can list carbon numbers such as methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, sec-butyl alcohol, the tert-butyl alcohol is 1～4 alkanols; Amide-type such as dimethyl formamide, dimethylacetylamide; Ketone such as acetone, DAA or keto-alcohol; Ethers such as oxolane, dioxane; Poly-alkane glycols such as polyethylene glycol, polypropylene glycol; Ethylene glycol, propane diols, butanediol, triethylene glycol, 1,2, alkylidenes such as 6-hexanetriol, sulphur two glycerine, hexylene glycol, diethylene glycol comprise the alkylene glycol class of 2～6 carbon atoms; Lower alkyl ether acetic acid esters such as poly glycol monomethyl ether acetic acid esters; Glycerine; The lower alkyl ethers of polyalcohols such as glycol monomethyl first (or second) ether, diethylene glycol first (or second) ether, triethylene glycol list first (or second) ether; Polyalcohol such as trimethylolpropane, trimethylolethane; N-N-methyl-2-2-pyrrolidone N-, 2-Pyrrolidone, 1.3-dimethyl-2-imidazolidinone etc.Above-mentioned water-miscible organic solvent can use separately or use as mixture.In addition, water preferably uses deionized water (ion exchange water).
The not special restriction of the content of the water-miscible organic solvent that is comprised in the ink of the present invention is preferably 3 quality %～50 quality % with respect to the ink total amount.In addition, the content of water is 50 quality %～95 quality % with respect to the total amount of ink, is preferably below the 82 quality %, more preferably below the 77 quality %, is preferably especially below the 72 quality %.
In addition, the water-soluble organic compounds that is comprised in the ink is the same with fluid composition, difference by the water holding capacity under the environment of the water holding capacity under the environment that comprise 23 ℃ of temperature, humidity 45% and 30 ℃ of temperature, humidity 80% is the water-soluble organic compounds below 36% more, can further alleviate ink curling after being applied on the recording medium.
(other composition)
In ink of the present invention, except mentioned component, can add NMF as required, in order to keep desirable rerum natura, can also in the scope of not damaging target effect of the present invention, add surfactant, defoamer, anticorrisive agent, mould inhibitor etc., and obtain to add the effect of being brought.
(tone of ink)
Constituting the not special restriction of tone of the ink of complete fluid composition and ink, can be for example to demonstrate the ink that is selected from least a tone in yellow, magenta, cyan, redness, green, blueness and the black.Specifically, can be by the above-mentioned colorant of suitable selection so that form the ink of required tone.Content about the colorant of each ink, under the situation that for example is used for ink mist recording, it is just passable that above-mentioned ink has good ink-jet spray characteristic, in addition, can suitably select content so that have desirable tone or concentration, for example, with respect to the ink gross mass, be preferably 1 quality %～50 quality %.In addition, the content of water is preferably 50 quality %～95 quality % with respect to the gross mass of ink.
In addition, the ink that is used in combination with fluid composition is not limited to a kind, more preferably makes the ink set that is fit to form coloured image by the ink that makes up different tones more than 2 kinds.In this case, in ink more than 2 kinds, at least a ink can get final product with the fluid composition reaction.
In constituting the ink of ink set, at least a kind of effect that is colorant by ionic group is dispersed in the ink in the aqueous medium, and other ink can be to comprise the ink of dyestuff as colorant.Certainly, also can be that effect that whole inks all is a colorant by the water-based group is dispersed in the ink in the aqueous medium.If such ink set, then can be suppressed to form by ink discharge device becomes inks problem, different tones bleeding during adjacent applying on recording medium under the situation of coloured image.
More particularly, in the ink-jet coloured image, become the bleeding generation especially significantly between black and other color inks (for example being selected from least a ink of yellow ink, magenta ink, cyan, red ink, green ink and blue ink) easily of problem.Therefore, preferred compositions use effect by ionic group make colorant be dispersed in aqueous medium, and can with the fluid composition black ink that ground constitutes that interacts.And, in other color inks, can be formed in the ink of dissolving dye in the aqueous medium, certainly the same with black ink, the effect that can make by ionic group is dispersed in ink in the aqueous medium with colorant.
[complete fluid composition and ink]
The inventor is in order further to improve curling of the record thing that obtains by two liquid systems that use liquid and ink to form image, carried out further research, found that, by making the ink and the fluid composition that are applied on the recording medium satisfy following condition, can suppress curling of resulting records thing effectively.
(condition)
800 times of dilute aqueous solution 50g of described fluid composition and 5 times of dilute aqueous solution 0.3g of described ink are mixed, after filtering with the filter of 0.2 μ m after 15 minutes, absorbance under the maximum absorption wavelength (using under the situation of carbon black as pigment wavelength 550nm) of visible region is designated as (A); When 5 times of dilute aqueous solution 0.3g of described ink and the absorbance of mixed solution under the maximum absorption wavelength of visible region of pure water 50g are designated as (B), (A) with (B) satisfy following relation.
(A)/(B)＜0.85
Can more effectively prevent the mechanism of curling about the record thing that uses above-mentioned such fluid composition that limits and ink to obtain, the inventor infers as follows.The above-mentioned relation formula has been stipulated the reagency of fluid composition and ink.Regulation is reactive as described above, the aggregation that generates that contacts by the colorant that comprised in the polyvalent metal ion that comprised in the fluid composition and the ink is present on the recording medium superficial layer part mostly, therefore can be suppressed at and apply the cellulosic contraction that causes after the moisture.
[ink-jet recording apparatus]
Then, provide an example that is used to use aforesaid liquid composition and/or above-mentioned ink formation record images device.
Fig. 1 is the cut-away section schematic diagram of an example of ink-jet recording apparatus.This image processing system adopts the serial type ink-jet recording, therefore, the paper feeding cassette 16 that the sheet feed stacker 17 that comprise record head 1, is used to supply recording medium (below be sometimes referred to as record-paper) 19 and the parts integration that is used to be coated with fluid composition of the present invention form, make record head along reciprocating driver part of the direction vertical and the control assembly of controlling the driving of these inscapes with the throughput direction of record-paper.
The record-paper 19 that is separated paper supply be by large diameter intermediate calender rolls 12 and with the applicator roll 6 of the minor diameter of its crimping, carry along the conveyor surface of paper feeding cassette 16 and the conveyor surface of paper guider 27.These conveyor surfaces are by constituting with the face that intermediate calender rolls 12 is drawn the bending of isocentric circular arc.Thereby, record-paper 19 from these conveyor surfaces by and with the counter-rotating of its throughput direction.That is, the printing surface of record-paper 19 till being transported to intermediate calender rolls 12 from sheet feed stacker 17, printing surface all down, but in record-oriented head 1, printing surface (writes down first side) up.Therefore, the printing surface of record-paper is usually towards the lateral direction of image processing system.
Fluid composition coating parts are arranged in the paper feeding cassette 16, and comprise that state that the supplemental tank 22 that is used for feeding liquid composition 15 and a part with periphery be immersed in above-mentioned groove 22 by intermediate calender rolls 12 that supports and the applicator roll 6 that is provided with above-mentioned intermediate calender rolls with paralleling and contacts with intermediate calender rolls 12 and rotate to same direction with rotating freely.In addition, applicator roll 6 contacts with periphery with the intermediate calender rolls 12 that is used for feeding recordable paper 19 and is parallel.Therefore, when feeding recordable paper 19, along with the rotation of intermediate calender rolls 12, intermediate calender rolls 12 and applicator roll 6 rotate.Its result, fluid composition 15 is supplied to by feed rolls 13 on the periphery of applicator roll 6, further is uniformly applied on the printing surface of the record-paper 19 that applied roller 6 and intermediate calender rolls 12 clampings by applicator roll 6.
In addition, in this ink-jet recording apparatus, in supplemental tank 22, be provided with float 14.This float 14 is a kind of materials than fluid composition 15 light specific gravities, by seeing through the surplus display window 21 as transparent component on the liquid level that swims in fluid composition, can comprise the surplus of the fluid composition of reacted constituent from outside Visual Confirmation.
Fig. 2 is the figure that sees the surplus display part from the front.The surplus display part is along the mark that is vertically arranged with expression surplus degree of surplus display window 21.Among the figure, when the liquid level of fluid composition or float 14 arrive the position that " expire " identify, be the state of tankful.On the other hand, express liquid composition residue is less when the liquid level of fluid composition or buoy 14 arrive the position of " adding " sign.Therefore, fluid composition 15 slowly reduces, can the liquid make-up composition when float 14 is reduced to " adding " line, come into plain view like this.
The compensation process of fluid composition as shown in Figure 3, under with the state of paper feeding cassette 16 when image forming device body is extracted out, be inserted in the injection port that rubber components constituted 20 with opening portion by front end fluid composition is expelled in the supplemental tank 22 instrument used for injection 23.
Like this, the record-paper that has been coated with the ormal weight of fluid composition is being transported to recording section by main conveying roller 7 with the hold-down roller 8 of its crimping thereafter, is recorded 1 and applies ink.Record sheet 19 in above structure by paper supply, after printing is discharged from conveying by exit roller 3 with the ratchet 4 of its crimping, on the row's of being stacked on paper disc 5.
In addition, applying under the situation of fluid composition by roller etc., particularly when the viscosity of fluid composition is higher than the viscosity of ink, with a spot of applied amount instabilityization ink effectively just, and the anchorage of record thing etc. is also good, so preferably.More particularly, the viscosity of fluid composition is high more, the easier top that rests on recording medium of polyvalent metal ion then, thereby react with ink effectively easily.
On the other hand, after ink and fluid composition reaction, the colorant composition in the preferred ink rests on the top of recording medium, rapid permeability such as solvent and water is in recording medium, promptly carry out Separation of Solid and Liquid rapidly, thereby from writing down the viewpoints such as anchorage of thing, preferred viscosities is lower.The viscosity of the aforesaid liquid composition when applying fluid composition by roller etc. is preferably 3mPas～100mPas, more preferably 5mPas～60mPas.The viscosity of fluid composition of the present invention or ink is the value of measuring by conventional method under 25 ℃.
In Fig. 4, shown another example of ink-jet recording apparatus.In Fig. 4, the 61st, as the scraper plate of wiper member, the one end is maintained fixed by the scraper plate holding member, forms cantilever position.Scraper plate 61 is arranged on the posting field position adjacent that is determined with record head 65, in addition, under the situation of present embodiment, is held with the state in the mobile route that is projected into record head 65.
62 is the lid of the outstanding actinal surface of record head 65, and its structure is: be arranged on the home position with scraper plate 61 adjacency, and move along the direction vertical with the moving direction of record head 65, with ink jet exit face butt, it is covered.In addition, 63 are and the ink absorber of scraper plate 61 in abutting connection with setting, the same with scraper plate 61, are held with the state in the mobile route that is projected into record head 65.Constitute by above-mentioned scraper plate 61, lid 62 and ink absorber 63 and to spray reciprocating parts 64, spray the removing of moisture, dust etc. of actinal surface by scraper plate 61 and ink absorber 63.In addition, utilize not shown pump to attract the ink of record head by lid, and then attract to be positioned at the ink etc. of the jet of fluid composition, thereby the recovery system unit of the original jet performance of the original ink of composition recovery record head or ink and fluid composition.
The 65th, have and spray energy producing unit, be equipped with ink being ejected into of jet over against the record head of the enterprising line item of recording medium that sprays actinal surface, 66 for having carried record head 65 and being used to carry out the balladeur train that moves of record head 65.Balladeur train 66 engages slidably with guidance axis 67, the part of balladeur train 66 and 69 (not shown)s that link together of being with that drive by motor 68.Like this, balladeur train 66 can move along guidance axis 67, and can record head 65 determined posting fields and with it the zone of adjacency move.51 for being used to insert the paper-supply section of recording medium, and 52 are the paper feed roller by not shown motor driving.
By these structures, recording medium is transported on the position of facing with the injection actinal surface of record head 65, and along with being transported on the row's paper part that is provided with exit roller 53 of writing down.In said structure, when record head 65 stops record and gets back on the home position, spray the lid 62 of recovered part 64 and keep out of the way from the mobile route of record head 65, scraper plate 61 then is projected in the mobile route.The result is that the jet of record head 65 obtains wiping.In addition, when lid 62 covered it with the jet face butt of record head 65, lid 62 moved in the mode in the mobile route that is projected into record head.Record head 65 from the home position when move the record start position, on the identical position, the position of lid 62 when being in above-mentioned wiping with scraper plate 61.The result is that in this moved, the injection actinal surface of record head 65 also obtained wiping.
Above-mentioned record head to the home position move not only in the end of record time or spray when recovering and take place, and record head the posting field that is used to write down move during with the interval of regulation to moving with the home position of posting field adjacency, and be accompanied by this and move and carry out above-mentioned wiping.
Fig. 5 is for supplying with ink or not containing the parts of the fluid composition of colorant to record head, for example, held the schematic diagram of an example of the box 45 by pipeline ink supplied or fluid composition.Wherein, 40 for to hold the hold parts of supply with ink or fluid composition, and for example, sack is provided with the bolt 42 of rubber system at its front end.By in this bolt 42, inserting the pin (not shown), ink in the sack 40 or fluid composition can be supplied to record head.44 for being held the absorber of useless ink or waste liq composition.As accommodating part 40, with the liquid contact surface of ink or fluid composition preferably by polyolefin, particularly polyethylene forms.Such box, for example as shown in Figure 4, its structure is that the record head 901 that sprays ink or fluid composition is removably constituted, and simultaneously, is installed under the state of record head at above-mentioned box 45, ink or fluid composition are fed into record head 901.
[ink characteristics; The ink-jet spray characteristic, to the permeability of recording medium]
Complete fluid composition of the present invention and ink are particularly suitable for ink mist recording.As ink jet recording method, comprise ink is applied the mechanics energy and the recording method of liquid droplets, and ink applied heat energy and by the recording method that the foaming of ink comes liquid droplets, not only can use ink of the present invention in these recording methods, and can use fluid composition.At this moment, the fluid composition formed of the invention described above and ink preferably have the characteristic that can spray from ink gun.Viewpoint based on the characteristic of spraying from ink gun is considered, the characteristic of these liquid, for example its viscosity is preferably 1～15mPas, and surface tension is preferably more than the 25mN/m (dyne/cm), special preferred viscosities 1～5mPas, surface tension 25～50mN/m (dyne/cm).In addition, fluid composition of the present invention must be only on recording mediums such as paper reacts with specific ink, therefore, preferably the surface tension of fluid composition is controlled in the scope that to spray from ink gun, and, liken to for the surface tension of the ink of the object by the fluid composition instabilityization is bigger, so that fluid composition can not be penetrated into other positions at the record position that is not particular ink.
Embodiment
Below, use embodiment and comparative example that the present invention is carried out more specific description, still, in being no more than the scope of its theme, the present invention is not subjected to any restriction of following embodiment.In addition, in following description, if there be not special the qualification, part, % are benchmark with the quality.
[evaluation of fluid composition]
(preparation of fluid composition)
Various compositions shown in the following table 1 being mixed, fully stir and dissolve, is that the micro-filter (manufacturings of the Off ィ of Fuji Le system) of 1 μ m carries out pressure filtration by the aperture then, prepares fluid composition 1～7.In addition, unit is quality %.
Table 1
| Water holding capacity poor | Molecular | Fluid composition | ||||||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | ||||||||||
| Trimethylolpropane | 18.0 | 134.2 | 16.0 | 15.0 | 10.0 | 15.0 | 15.0 | |||||||||
| N, N-pair-(2-ethoxy)-urea | 27.4 | 148.2 | 16.0 | 15.0 | ||||||||||||
| Glycerine | 49.2 | 92.1 | 14.0 | 14.0 | 2.0 | 2.0 | 5.0 | 15.0 | ||||||||
| Ethylidene-urea | 52.4 | 86.1 | ||||||||||||||
| Calcium nitrate tetrahydrate | - | - | 6.0 | 6.0 | 6.0 | 6.0 | 6.0 | 6.0 | 6.0 | |||||||
| ア セ チ レ ノ one Le EH (*) | - | - | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | |||||||
| Ion exchange water | - | - | 63.0 | 63.0 | 76.0 | 76.0 | 78.0 | 63.0 | 78.0 | |||||||
| Y/X | 0.88 | 0.88 | 0.13 | 0.13 | 0.50 | 1.00 | 0.00 | |||||||||
(*) the acetylenediol ethylene oxide adduct (surfactant) that fine chemistry industry is made is ground in the river
In addition, the moisture conservation rate of calcium nitrate tetrahydrate that is comprised in the above-mentioned composition and ア セ チ レ ノ one Le EH is less than 5%.
(evaluation of curling)
Use has according to tracer signal ink is applied the many jet recording device of request service type that heat energy sprays ink, and resulting fluid composition 1～7 is applied on the recording medium.In addition, employed ink-jet recording apparatus, per 1 emitted dose are 2.8pL, have the packing density of 2400 * 1200dpi that drive condition is for using the device of driving frequency as 10kHz, PPC in the A4 size uses on the paper (Canon's manufacturing), evenly applies until applied amount to reach 2.4g/m
2The evaluation method of curling is as described below.
Curling evaluation method
With printed product under the condition of 24 ℃ of temperature, humidity 50%, after printing immediately (in 1 minute), after 1 hour, placed 1 day, 2 days, 3 days, 7 days after, in time through measuring amount of curl.The situation of curling as the recessed direction of the principal direction of printed product is designated as+(just curling), and the situation of curling to convex direction is designated as-(negative curling), uses ruler to measure distance from the front end of the paper that curls to the ground plane of paper.The judgment standard that curls is as follows.Evaluation result is as shown in table 2.
AA the: in ± 10mm
A: greater than ± 10mm, but in ± 25mm
B: greater than ± 25mm, but in ± 40mm
C: the front end of paper is translated into the state of paper inboard
D: the front end of paper is rolled onto the state of paper inboard
(evaluation of jetting stability)
Use has according to tracer signal ink is applied the many jet recording device of request service type that heat energy sprays ink, and resulting fluid composition 1～7 is applied on the recording medium.In addition, employed ink-jet recording apparatus, per 1 emitted dose are 2.8pL, have the packing density of 2400 * 1200dpi that drive condition is for using the device of driving frequency as 10kHz, PPC in the A4 size uses on the paper (Canon's manufacturing), prints to make that printing ratio reaches 100%.In addition, carried out 2 steps of printing sector scanning 2 times are printed.In addition, the print state of the fluid composition that applies in order to confirm adds C.I. direct blue 199 as colouring agent in fluid composition.The addition of colouring agent is not for influencing the trace that spray characteristic is estimated.
Jetting stability 1 (jetting stability after injector head is placed) evaluation method
As the evaluation of the jetting stability of fluid composition, in order to confirm to have or not the problems such as obstruction that produce nozzle, the aforesaid liquid composition is contained in the ink gun placed 1 month, print problem such as confirm to have or not the disorder that produces image, blur then.The benchmark of jetting stability 1 (jetting stability after injector head is placed) is as follows.Evaluation result is as shown in table 2.
A: do not occur fuzzy
B: have slightly fuzzy, but no problem basically level
C: occur bluring the in-problem level of image
D: can't spray
Jetting stability 2 (starting characteristic) evaluation method
As the evaluation of the jetting stability of fluid composition, at environment 1: often wet and normal temperature, and environment 2: 15 ℃ of temperature, humidity are confirmed for 10% time to have or not when beginning to print and are produced the disorder of printing the beginning part, fuzzy.The benchmark of jetting stability 2 (starting characteristic) is as follows.Evaluation result is as shown in table 2.
A: do not occur fuzzy
B: occur bluring, image has disorder slightly, but no problem basically level
C: the beginning part disorder, the in-problem level of image
D: the beginning part is very fuzzy
Table 2
| Fluid composition | Curl and | Jetting stability | 1 | | ||||||||
| Immediately | After 1 hour | After 1 day | After 2 days | After 3 days | After 7 | Environment | 1 | | ||||
| | 1 | 1 | AA | AA | AA | A | A | B | | B | D | |
| 2 | 2 | AA | AA | AA | A | A | B | | B | C | ||
| 3 | 3 | AA | AA | A | A | A | A | B | B | B | ||
| 4 | 4 | AA | AA | A | A | A | A | B | B | D | ||
| Comparative example | 1 | 5 | A | A | B | B | B | C | | B | D | |
| 2 | 6 | AA | A | A | B | C | C | B | B | D | ||
| Reference example | 1 | 7 | AA | AA | AA | A | A | A | D | B | D | |
(evaluation of the property separated out during water evaporates)
Various compositions shown in the following table 3 are mixed, fully stir and dissolve, using the aperture then is that the micro-filter (manufacturings of the Off イ of Fuji Le system) of 1 μ m carries out pressure filtration, prepares fluid composition 8 and 9.In addition, unit is quality %.
Table 3
| Moisture holding capacity poor | Molecular weight | Fluid composition | ||
| 8 | 9 | |||
| Trimethylolpropane | 18.0 | 134.2 | 16.0 | 16.0 |
| N, N-pair-(2-ethoxy)-urea | 27.4 | 148.2 | ||
| Glycerine | 49.2 | 92.1 | 14.0 | |
| Ethylidene-urea | 52.4 | 86.1 | 14.0 | |
| Calcium nitrate tetrahydrate | - | - | 18.0 | 18.0 |
| ア セ チ レ ノ one Le EH (*) | - | - | 1.0 | 1.0 |
| Ion exchange water | - | - | 51.0 | 51.0 |
| Y/X | 0.88 | 0.88 | ||
(*) the acetylenediol ethylene oxide adduct (surfactant) that fine chemistry industry is made is ground in the river
With resulting fluid composition 8 and 9 and fluid composition 1～7 each 5g of above-mentioned preparation put into culture dish and measure, after under the environment of 25 ℃ of temperature, humidity 30%, placing 30 days, by the state of visualization fluid composition, the property separated out during to the water evaporates in the fluid composition is estimated.Evaluation result is as shown in table 4.
Table 4
| Fluid composition | Have or not precipitate |
| 1 | Do not have |
| 2 | Do not have |
| 3 | Do not have |
| 4 | Do not have |
| 5 | Do not have |
| 6 | Do not have |
| 7 | Have |
| 8 | Do not have |
| 9 | Have |
[evaluation of curling of the record thing that obtains with two liquid systems]
Then, confirm for the curling of resulting records thing in the system that after applying fluid composition, applies ink (two liquid systems).
(preparation of ink)
Be prepared as follows described pigment dispersion 1 and 2.Use resulting pigment dispersion 1 and 2, the preparation paint ink.In the modulation of paint ink, mix each composition according to following table 5, fully stir, using the aperture then is that the film filter (manufacturings of the Off ィ of Fuji Le system) of 0.3 μ m carries out pressure filtration, prepares ink 1～3.
Will be as 10 parts of the Monarch 880 (manufacturing of Cabot company) of pigment, anionic species macromolecule P-1 (styrene/M230G (methoxy polyethylene glycol methacrylate-styrene polymer: Xin Zhong village chemical company makes)/acrylic copolymer (copolymerization ratio (mass ratio)=65/12/25), acid number 160, weight average molecular weight 8000,40 parts of the aqueous solution of solid constituent 10% (nertralizer: potassium hydroxide)), 50 parts of mixing of pure water, join batch (-type) vertical grinding machine (AIMEX manufacturing), fill 250 parts of zirconium oxide beads that diameter is 0.3mm, carry out water-cooled on one side, Yi Bian carry out 10 hours dispersion treatment.And then, by centrifugal separator big particle is removed from this dispersion liquid.And,, obtain that solid constituent is about 14.0%, weight average particle diameter is the pigment dispersion 1 of 110nm as final prepared product.
Will be as 10 parts of Monarch 880 (manufacturing of Cabot company), anionic species macromolecule P-2 (styrene/acrylic acid co-polymer (copolymerization ratio (mass ratio)=70/30), acid number 180, weight average molecular weight 10000, the aqueous solution of solid constituent 10%, the nertralizer: potassium hydroxide) 40 parts, 50 parts of mixing of pure water of pigment, join batch (-type) vertical grinding machine (AIMEX manufacturing), fill 150 parts of zirconium oxide beads that diameter is 0.3mm, carry out water-cooled on one side, Yi Bian carry out 10 hours dispersion treatment.And then, by centrifugal separator big particle is removed from this dispersion liquid.And,, obtain that solid constituent is about 14%, weight average particle diameter is the pigment dispersion of 110nm as final prepared product.(aqueous solution (nertralizer: potassium hydroxide)) of styrene/acrylic acid co-polymer (copolymerization ratio (mass ratio)=87/13), acid number 100, weight average molecular weight 11000, solid constituent 10% obtains pigment dispersion 2 to add 30 parts of anionic species macromolecule P-3 in above-mentioned dispersion.
Table 5
| Water holding capacity poor | | Ink | ||||||
| 1 | 2 | 3 | ||||||
| Pigment dispersion 1 | - | - | 40.0 | 40.0 | ||||
| Pigment dispersion 2 | - | - | 40.0 | |||||
| Cetomacrogol 1000 | 18.9 | 1000 | 5.0 | 5.0 | 5.0 | |||
| Glycerine | 49.2 | 92.1 | 5.0 | |||||
| Diethylene glycol | 39.7 | 118.2 | 5.0 | 7.5 | 7.5 | |||
| Trimethylolpropane | 18.0 | 134.2 | 3.0 | 3.0 | ||||
| ア セ チ レ ノ one Le EH (*) | - | - | 1.0 | 1.0 | 1.0 | |||
| Ion exchange water | - | - | 44.0 | 43.5 | 43.5 | |||
(*) the acetylenediol ethylene oxide adduct (surfactant) that fine chemistry industry is made is ground in the river
(with two liquid systems manufacturings record thing)
Use the applicator roll of structure shown in Figure 1, fluid composition 8 is applied on the recording medium by rolling method.In addition, adjust the speed and the contact pressure of roller of roller, so that fluid composition reaches 2.4g/m to the coating weight of recording medium to recording medium
2In addition, recording medium uses the PB paper (A4 size) that Canon Inc. makes.
After the coating liquid composition, use immediately to have ink is applied the many jet recording device of request service type that heat energy sprays ink according to tracer signal, apply ink 1～3, carry out following evaluation.In addition, employed ink-jet recording apparatus, per 1 emitted dose is 2.8pL, has the packing density of 2400 * 1200dpi that drive condition prints and makes that printing ratio reaches 100% for to use the device of driving frequency as 10kHz on the recording medium that has applied fluid composition 8.In addition, carried out 2 steps of printing sector scanning 2 times are printed.
(reactivity of ink and fluid composition)
Use following complete fluid composition and ink, mix under the following conditions, measure absorbance, carry out reactive evaluation.The result is as shown in table 6 below.
800 times of dilute aqueous solution 50g of aforesaid liquid composition and 5 times of dilute aqueous solution 0.3g of above-mentioned ink are mixed, after the filter filtration with 0.2 μ m after 15 minutes, absorbance under 550nm is designated as 5 times of dilute aqueous solution 0.3g of (A), above-mentioned ink and the absorbance of mixed solution under 550nm of pure water 50g is designated as (B), obtains the value as (A)/(B) of reactive indices.
Table 6
| Fluid composition | Ink | Reactive (A)/(B) |
| 8 | 1 | 0.38 |
| 8 | 2 | 0.38 |
| 8 | 3 | 0.78 |
(evaluation of curling)
The evaluation method of curling is identical during with the use fluid composition.Evaluation result is as shown in table 7 below.
Table 7
| Fluid composition | Ink | Curl and estimate | |||||||
| After 1 hour | After 1 day | After 2 days | After 3 days | After 7 | |||||
| Embodiment | |||||||||
| 5 | 8 | 1 | A | B | | B | C | ||
| 6 | 8 | 2 | A | A | | B | C | ||
| 7 | 8 | 3 | A | B | B | C | C | ||
| Reference example | 2 | 8 | - | AA | AA | A | A | B | |
| 3 | - | 1 | B | C | C | C | D | ||
| 4 | - | 2 | B | B | B | C | D | ||
| 5 | - | 3 | B | B | B | C | D | ||
In addition, the curling result of reference example 2 compares with the result of embodiment 4, and from printing began evaluation after 1 day, the result was good.
Claims (13)
1. fluid composition that is used for image recording process, this image recording process possesses: apply with dissolved state on recording medium or comprise the operation of the ink of colorant with dispersity, and the operation that described recording medium is applied fluid composition, this fluid composition is by contacting dissolved state or the dispersity instabilityization that makes the colorant in the described ink with ink, it is characterized in that, described fluid composition comprises polyvalent metal ion at least, water, water-soluble organic compounds 1 and water-soluble organic compounds 2, and, the content X (quality %) of described water-soluble organic compounds 1 is more than the 15 quality % with respect to the fluid composition total amount, and described water-soluble organic compounds 1 satisfies following relational expression with respect to the content X (quality %) of fluid composition total amount and described water-soluble organic compounds 2 with respect to the content Y (quality %) of fluid composition total amount:
0＜Y/X≤0.9
Water-soluble organic compounds 1 be a kind of under the environment of 23 ℃ of temperature, humidity 45% water holding capacity and the difference of the water holding capacity under the environment of 30 ℃ of temperature, humidity 80% be water-soluble organic compounds below 36%, that have water-retaining property,
Water-soluble organic compounds 2 is a kind of water-soluble organic compounds except that colorant and water-soluble organic compounds 1.
2. fluid composition according to claim 1, wherein, described water-soluble organic compounds 2 is Y＜15 quality % with respect to the content Y (quality %) of fluid composition total amount, and described water-soluble organic compounds 1 is selected from polyalcohol, amide compound.
3. fluid composition according to claim 1 and 2, wherein, water-soluble organic compounds 1 is the polyalcohol with amido link, and the molecular weight Mw of water-soluble organic compounds 1 is positioned at the scope of 100≤Mw≤1000.
4. according to each described fluid composition of claim 1～3, wherein, at least one in described water-soluble organic compounds 1 and the water-soluble organic compounds 2 is liquid down at normal temperature (25 ℃).
5. according to each described fluid composition of claim 1～4, wherein, the content of water (quality %) is below the 71 quality % with respect to the fluid composition total amount.
6. complete fluid composition and ink is characterized in that, described fluid composition is each described fluid composition of claim 1～5.
7. complete fluid composition according to claim 6 and ink are complete fluid composition and the inks that satisfies following condition:
5 times of dilute aqueous solution 0.3g of 800 times of dilute aqueous solution 50g of described fluid composition, described ink are mixed, after the filter filtration with 0.2 μ m after 15 minutes, maximum absorption wavelength at visible region (is using under the situation of carbon black as pigment, wavelength is 550nm) under absorbance be designated as (A), when 5 times of dilute aqueous solution 0.3g of described water-base ink and the absorbance of mixed solution under the maximum absorption wavelength of visible region of pure water 50g are designated as (B), (A) with (B) satisfy following relational expression:
(A)/(B)＜0.85。
8. an ink-jet recording apparatus is characterized in that, is equipped with claim 1～5 each described fluid composition and ink.
9. image forming method is the image recording process that comprises following operation: apply with dissolved state on recording medium or comprise the operation of the ink of colorant with dispersity; And described recording medium applied the operation of fluid composition, this fluid composition is characterized in that by contact dissolved state or the dispersity instabilityization that makes the colorant in the described ink with ink,
Described fluid composition comprises polyvalent metal ion, water, water-soluble organic compounds 1 and water-soluble organic compounds 2 at least, and, the content X (quality %) of described water-soluble organic compounds 1 is more than the 15 quality % with respect to the fluid composition total amount, and described water-soluble organic compounds 1 satisfies following relational expression with respect to the content X (quality %) of fluid composition total amount and described water-soluble organic compounds 2 with respect to the content Y (quality %) of fluid composition total amount:
0＜Y/X≤0.9
Water-soluble organic compounds 1 be a kind of under the environment of 23 ℃ of temperature, humidity 45% water holding capacity and the difference of the water holding capacity under the environment of 30 ℃ of temperature, humidity 80% be water-soluble organic compounds below 36%, that have water-retaining property,
Water-soluble organic compounds 2 is a kind of water-soluble organic compounds except that colorant and water-soluble organic compounds 1.
10. image forming method according to claim 9, wherein, described water-soluble organic compounds 2 is Y＜15 quality % with respect to the content Y (quality %) of fluid composition total amount, and described water-soluble organic compounds 1 is selected from polyalcohol, amide compound.
11. according to claim 9 or 10 described image forming methods, wherein, water-soluble organic compounds 1 is the polyalcohol with amido link, and the molecular weight Mw of water-soluble organic compounds 1 is positioned at the scope of 100≤Mw≤1000.
12. according to each described image forming method of claim 9～11, wherein, at least one in described water-soluble organic compounds 1 and the water-soluble organic compounds 2 is liquid down at normal temperature (25 ℃).
13. according to each described image forming method of claim 9～12, wherein, the content of water (quality %) is below the 71 quality % with respect to the fluid composition total amount.
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| CN102991130A (en) * | 2011-09-15 | 2013-03-27 | 株式会社理光 | Image forming method and inkjet recording device using the same |
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| JP3991289B2 (en) * | 1995-08-31 | 2007-10-17 | セイコーエプソン株式会社 | Pigment-based ink composition capable of forming an image with less blur |
| JPH1178212A (en) * | 1997-07-16 | 1999-03-23 | Seiko Epson Corp | Ink jet recording method |
| JP2000247013A (en) * | 1998-12-28 | 2000-09-12 | Minolta Co Ltd | Method and device for ink recording |
| JP4132487B2 (en) * | 1999-10-19 | 2008-08-13 | 株式会社リコー | Ink set for inkjet recording |
| JP2002211106A (en) * | 2001-01-15 | 2002-07-31 | Ricoh Co Ltd | Ink jet recording method, recording liquid, ink set and recorded matter |
| JP2002332438A (en) * | 2001-05-10 | 2002-11-22 | Canon Inc | Inkset, ink cartridge, printing unit, method for forming colored part on medium to be printed and ink-jet printer |
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| CN102991130A (en) * | 2011-09-15 | 2013-03-27 | 株式会社理光 | Image forming method and inkjet recording device using the same |
| US8820875B2 (en) | 2011-09-15 | 2014-09-02 | Ricoh Company, Ltd. | Image forming method and inkjet recording device using the same |
| CN102991130B (en) * | 2011-09-15 | 2015-04-22 | 株式会社理光 | Image forming method and inkjet recording device using the same |
| CN103242703A (en) * | 2012-02-02 | 2013-08-14 | 株式会社理光 | Post-treatment liquid for inkjet recording, image forming method, cartridge and image forming apparatus |
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| US11577538B2 (en) | 2019-12-10 | 2023-02-14 | Seiko Epson Corporation | Ink jet recording method and ink jet recording apparatus |
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