CN101260258B - Liquid composition, image forming method, cartridge, recording unit and ink jet recording apparatus - Google Patents

Abstract

The present invention provides a liquid composition, an image forming method, an ink box, a recording unit and an ink jet recorder, in particular, to a liquid composition which can achieve superior scratch resistance of images at such a level that coloring materials are hardly scraped off even when images are scratched with finger nails under application of such strong pressure as to scratch a recording medium at its non-recorded areas. The liquid composition contains at least a modified siloxane compound having specific structure and a polymer whose acid value and hydrogen bond parameter (deltah) are specified.

Description

Liquid compsn, image forming method, print cartridge, record cell and ink-jet recording device

Technical field

The present invention relates to the liquid compsn that adopts pigment to use as the pigment inks of colorant, and the ink-jet recording device that also relates to the image forming method, print cartridge, record cell and this liquid compsn of employing that are applicable to ink jet recording method.

Background technology

Be used for the China ink of ink-vapor recording, adopting to contain the image of pigment as the pigment inks formation of colorant, containing dyestuff with employing and compare as the image of the dye ink formation of colorant, the soundness of photostabilization or ozone resistance etc. is good.On the other hand, there is a problem in the image that forms with pigment inks, promptly compares with the image that forms with dye ink, and when waiting the wiping image with finger, colorant is wiped, that is, their anti-wipings are poor.

To this problem, for how to protect document image to propose a plurality of schemes through on image, carrying out the application surface coating.For example, the someone proposes on image hot transfer printing resist transfer printing sheet and protects the scheme of image (referring to the open No.2000-153677 of Japanese patent application, being called " patent documentation 1 " here).In addition, the someone proposes the scheme (referring to the open No.2003-170650 of Japanese patent application, being called " patent documentation 2 " here) through image being heated simultaneously and pressurizeing and protect image.The somebody proposes, and on the image that adopts pigment inks to form, contains the scheme (referring to open No.2004-99766 of Japanese patent application and No.2005-81754, being called " patent documentation 3 and 4 " here respectively) of can the film forming compound of shape protecting image through giving.

Yet; The image of outdoor displaying, for example institutes such as pictorial poster, picture poster, sign, literature and art advertisement require the sufficiently high level of anti-wiping, as traditional prior art; When adopting finger to wait the wiping image, it is fully not enough that colorant reaches the degree of not wiping.

For example, when printing pictorial poster and advertisement, often adopt sizable recording medium, for example A0 size and A1 size have formed the record images medium and when transportation, generally will be rolled into tubular.Therefore, produce following point.When curling recording medium, the edge section of recording medium is edges and corners for example, and image possibly abraded.In this case, even when using general pigment inks, think to reach high-caliber image scuff resistance, but the image that forms abraded, cause colorant to be wiped.Such problem possibly take place with quite high frequency.Also occur under other situation with this problem similar problem.For example, in this case, when the image that adopts pigment inks to form sticks on when outdoor as pictorial poster, this image by some sharp keen device for example nail carry out strong wiping and happen occasionally.This situation and above-mentioned same, the problem that colorant is wiped takes place with quite high frequency.

For head it off, can adopt disclosed method in the patent documentation 1, improve resist intensity or strengthen bed thickness as adopting, then perhaps can reach the object of the invention.Yet, under the situation like disclosed method in patent documentation 1 and 2, the device or the hot-rolling that carry out hot transfer printing must be arranged, make device complicated, therefore, this is unfavorable.On the other hand, in recent years, require the exploitation aqueous ink, this aqueous ink can obtain having high anti-abrasive image with original comparing, and promptly uses sharp keen device contacts images such as nail, and the colorant of image is not wiped yet.

When adopting pigment inks to be used for ink-vapor recording, when forming image, improving the related scheme of scuff resistance of image, except that above-mentioned 4 patent documentations, a plurality of schemes are proposed also.Yet,,, obtain all not take place the scuff resistance of scratch level with finger contact history medium even be through the optimum that adopts any a kind of such technology to realize according to inventor's research.

For example, in patent documentation 3 and 4, smear liquid or clear ink introducing water-soluble polymers to the top.Yet; The inventor's result of study shows; Though contain multiple effective polymkeric substance that improves the image scuff resistance in the liquid compsn, the improvement of image scuff resistance only reaches certain level, because the bounding force between recording medium, polymkeric substance and the pigment only depends on polymer property.That is, in patent documentation 3 and 4 inventions disclosed, the image scuff resistance is improved the characteristic equally only depend on polymkeric substance, and both the category of transnormal scuff resistance did not reach the scuff resistance level as the object of the invention yet.In more detail; These technology; Do not reach high-level scuff resistance, so that the high-level scuff resistance of " to the non-recording section of recording medium, apply the crunch of giving the scratch size; when abrading through sharp keen devices such as nails, colorant is difficult to wiped " does not reach yet as the object of the invention.Particularly when the content of the pigment solids composition in the China ink be that benchmark reaches 1.2 quality % or when lower with black total mass because few, so that only be difficult to obtain high scuff resistance as the object of the invention with polymkeric substance as the solid component content of filler.

The above results also can clearly can be known from the evaluation method of the embodiment of patent documentation 3 and 4.In more detail, in patent documentation 3, be placed on common paper on the image, and put specific weight above that friction images.In patent documentation 4, use the rubber friction images.That is, these evaluation methods when being used for friction images, are estimated deterioration degree, compare with scuff resistance level as the object of the invention, can think that the evaluation level is suitable demulcent.

In addition, in the invention of patent documentation 3 records, institute's consumption of the Topcoating liquid of protection image is 2 times or more times with respect to used China ink amount, fixedly needs considerable time but reach.To this, also can be that the fact of after 24 hours, carrying out obtains confirming from the scuff resistance evaluation test of the embodiment of patent documentation 3.In addition, when forming image on the recording medium with black receiving layer, the problem of generation is that when institute's consumption of liquid surpassed the ability of black receiving layer maintenance liquid, recording medium can not absorb liquid.That is, shown in the invention of patent documentation 3 records, institute's consumption of Topcoating liquid is unpractical considerably beyond being used to form the necessary China ink amount of image.

Summary of the invention

Therefore, the purpose of this invention is to provide a kind of liquid compsn, said composition satisfies for example anti-adhesive property and safety storage stability for example of ejection; Use to be suitable for ink-vapor recording; Simultaneously, improve the image scuff resistance that adopts pigment inks to form, to reach the high level that does not reach usually.Specifically; The present invention provides a kind of liquid compsn; Said composition can obtain a kind of image with high-caliber scuff resistance like this, promptly in addition apply with recording medium non-posting field can produce under the abrasive strong pressure with the nail scratch image time, colorant also is difficult to wipe.

Another object of the present invention provides a kind of image forming method, print cartridge, record cell and ink-jet recording device that is applicable to ink jet recording method, and this recording unit can obtain having the image of this high-caliber scuff resistance.

Can achieve the above object through following the present invention.Promptly; Liquid compsn of the present invention is the liquid compsn that contains modified siloxane compound and polymkeric substance at least, and this modified siloxane compound is at least a kind of the modified siloxane compound that is selected from modified siloxane compound with following formula (1) expression, representes with the modified siloxane compound of following formula (2) expression and with following formula (3); Above-mentioned polymkeric substance is selected from least a of following polymkeric substance: having acid number is 90mgKOH/g～150mgKOH/g, and the hydrogen bond item (δ h) that draws polymkeric substance through the monomer SP that constitutes polymkeric substance is 1.0cal ^0.5/ cm ^1.5～3.7cal ^0.5/ cm ^1.5Polymer A; And its acid number is greater than 150mgKOH/g～200mgKOH/g, and the hydrogen bond item (δ h) that draws polymkeric substance through the monomer SP that constitutes polymkeric substance is 1.0cal ^0.5/ cm ^1.5～1.5cal ^0.5/ cm ^1.5Polymer B.

Formula (1)

The weight-average molecular weight of the modified siloxane compound of formula (1) expression is 8000～30000, R in the formula (1) ₁The alkylidene group of expression carbonatoms 1～20, R ₂The alkyl of expression Wasserstoffatoms or carbonatoms 1～20, m representes 1～250, and n representes 1～100, and a representes 1～100, and b representes 0～100.

Formula (2)

The weight-average molecular weight of the modified siloxane compound of formula (2) expression is 8000～is lower than 50000, R in the formula (2) ₃The alkyl of representing Wasserstoffatoms or carbonatoms 1～20 respectively independently, R ₄Represent the alkylidene group of carbonatoms 1～20 respectively independently, p representes 1～450, and c representes 1～250, and d representes 1～100.

Formula (3)

The weight-average molecular weight of the modified siloxane compound of formula (3) expression is 8000～is lower than 50000, and HLB be 1～less than 7, R in the formula (3) ₅The alkyl of representing Wasserstoffatoms or carbonatoms 1～20 respectively independently, R ₆The alkylidene group of expression carbonatoms 1～20, q representes 1～100, and r representes 1～100, and e representes 1～100, and f representes 0～100.

Image forming method according to another embodiment of the present invention; This image forming method has to recording medium and applies the operation of pigment inks and apply the image forming method of the operation of liquid compsn to recording medium; It is characterized in that, adopt the aforesaid liquid compsn as this liquid compsn.

Print cartridge according to another embodiment of the present invention is to have the wherein print cartridge of the liquid compsn storage compartment of storing liquid compsn, it is characterized in that the liquid compsn that is stored in this liquid compsn storage compartment is the aforesaid liquid compsn.

According to the record cell of another embodiment of the present invention is to have the liquid compsn storage compartment of storing liquid compsn wherein and the record cell of the record-header of atomizing of liquids compsn therefrom; It is characterized in that the liquid compsn that is stored in the aforesaid liquid composition stores part is the aforesaid liquid compsn.

According to the ink-jet recording device of another embodiment of the present invention is to have the liquid compsn storage compartment of storing liquid compsn wherein and the jet recording device of atomizing of liquids compsn therefrom; It is characterized in that the liquid compsn that is stored in the aforesaid liquid composition stores part is the aforesaid liquid compsn.

Still the liquid compsn of further embodiment is the liquid compsn that contains polymkeric substance and modified siloxane compound according to the present invention; Wherein said modified siloxane compound is to be selected from least a in following: the modified siloxane compound of the modified siloxane compound of above-mentioned formula (1) expression, above-mentioned formula (2) expression and the modified siloxane compound of above-mentioned formula (3) expression; Make that with the formation of said liquid compsn the benchmark evaluation image that combines pigment inks to form with this liquid compsn can have 0.40 or lower kinetic friction coefficient.

According to the present invention, the image scuff resistance that forms with pigment inks can be much better than in the prior art always the scuff resistance as target.In more detail, according to the present invention, a kind of liquid compsn is provided; It can obtain the image of excellent scratch resistance; Its degree does, even that apply with the non-recording section to recording medium so that the such powerful pressure of scratch during down with the nail scratch image, colorant is wiped hardly.

According to another embodiment of the present invention; A kind of image forming method, print cartridge, record cell and ink-jet recording device that is applicable to ink jet recording method is provided, and this ink-jet recording device can be stablized provides a kind of above-mentioned very image of high-level scuff resistance that has that obtains.

From the statement with reference to the following specific embodiments of following accompanying drawing, other characteristics of the present invention will be more clear.

Description of drawings

Fig. 1 is the mimic diagram of expression scuff resistance test notion.

Fig. 2 is the skiagraph of record-header.

Fig. 3 is the cross-sectional view of record-header.

Fig. 4 is the record-header stereographic map that is equipped with a plurality of record-headers, and each of these a plurality of record-headers is record-header shown in Figure 2.

Fig. 5 is the stereographic map of one of ink-jet recording device example.

Fig. 6 is the skiagraph of print cartridge.

Fig. 7 is the stereographic map of one of record cell example.

Fig. 8 is the mimic diagram of one of record-header example.

Embodiment

Through preferred embodiment the present invention is described at length below.The maximum characteristics of the present invention are, adopt the liquid compsn that contains following particular polymers and specific modified siloxane compound and pigment inks (below, only claim " China ink " sometimes) simultaneously, thus, adopt the surface of the image that this China ink forms to polish.Result as imaging surface is polished is that with comparing of the scuff resistance of using generally black and the image that liquid compsn forms, the scuff resistance of image significantly improves.That is, the present invention is based on the new approaches that act on the frictional force between image and the material that contacts with this image (for example, nail), and only to utilize the film-forming properties of polymkeric substance to improve the thinking of scuff resistance different with the general technology that kind.Therefore,, a kind of image can be provided according to the present invention, though wherein with to recording medium at its non-recording section under that apply so that strong pressure scratch degree size during with the nail scratch image, not only colorant is not wiped, and, also residual hardly scar.

According to the inventor's result of study, have been found that image and any material (for example nail) that possibly contact with this image between the frictional force that produces, in other words, the slipperiness of imaging surface can use kinetic friction coefficient as index expression.Kinetic friction coefficient can adopt the scuff resistance test, measures through following method.Fig. 1 is the mimic diagram of explanation scuff resistance test.

In this test, as rubber 2-3, cause scratch causing under the abrasive state near nail with polymethylmethacrylate (PMMA) ball.Then, adopt surperficial trier (trade(brand)name HEIDON TRIBOGEAR type 14DR, Shinto Kagaku K.K. makes), produce scratch with following manner.Specifically, as shown in Figure 1, contact with imaging surface is vertical from the top the PMMA ball that has applied loading, be in the sample 2-2 on the worktable 2-1, move with given speed, to abrade.

The quality that is used for the metal insert of fastening rubber 2-3 is deducted with scale mechanism 2-5.Then, the scuff resistance of vertical load (weight 2-4) the evaluation map picture through being applied to imaging surface.When Stage microscope moved, the horizontal direction power that acts on the rubber 2-3 can be measured through the load cell 2-6 that is connected with metal insert.Can when mobile, measure kinetic friction coefficient with respect to the imaging surface of rubber from the horizontal direction power and the ratio of normal load power.

The inventor adopts aforesaid method on various images, to carry out the scuff resistance test, and studies in great detail.As a result of; Find when forming image on the recording medium with coating; As long as the kinetic friction coefficient of image is 0.40 or lower, more preferably 0.35 or lower, special preferred 0.30 or lower; Image just can reach the high-level scuff resistance of the object of the invention, and the lower limit of said kinetic friction coefficient is 0.00 or bigger.

Here the route of introducing is, for the kinetic friction coefficient that the image that formed by pigment inks is had is 0.40 or lower, the moity of the present invention that contains the liquid compsn of following particular polymers and specific modified siloxane compound through employing reaches.In order to reach the purpose of the invention described above, the inventor inquires into the liquid compsn that contains several modified siloxane compounds, and this modified siloxane compound it is generally acknowledged that the slipperiness to improving film coated surface is effective.Yet; Employing contains the kinetic friction coefficient of the image that the liquid compsn of any above-mentioned specific modified siloxane compound forms; Compare with the image kinetic friction coefficient that the liquid compsn that does not contain any above-mentioned modified siloxane compound forms, the result shows kinetic friction coefficient value indifference.That is,, can't reach as the kinetic friction coefficient of the object of the invention, and scuff resistance can not fully obtain even use the liquid compsn contain the modified siloxane compound that any inventor studied at all.Its reason still do not understand, even use the liquid compsn of the said modified siloxane compound that contains the slipperiness that is considered to effectively to improve film coated surface usually, why kinetic friction coefficient does not change the image of formation.Yet; The inventor infers the reasons are as follows: as stated; The aqueous medium that the modified siloxane compound that exists in the liquid compsn exists in liquid compsn infiltrates in the recording medium, and therefore, recording medium forms the state that no modified siloxane compound exists in its surface.

Therefore, the inventor remains in to how causing modified siloxane compound in the most liquid compsn that the recording medium surface is enterprising has gone discussion.Then, the inventor at first expects utilizing the synergy of the characteristic and the polymer property of modified siloxane compound.As a result of, being considered to following formation is to be suitable for reaching the object of the invention most, and has advanced research.This formation is to utilize the characteristic of the high modified siloxane compound of wetting ability; Make the pigment of absorption composing images or the polymkeric substance adsorption of modification silicone compounds of liquid compsn, make latter's modified siloxane compound be present in the formation on the recording medium with polymkeric substance.

At first, the inventor treats the polymkeric substance that is included in the liquid compsn and studies.As a result of, the conclusion that obtains of research is, can on recording medium, have certain high-intensity film by the fixed polymer formation, is selected from that at least a kind of polymkeric substance of polymer A with following character and polymer B is best suited for.Polymer A is, acid number is 90mgKOH/g～150mgKOH/g, and the hydrogen bond item (δ h) that obtains polymkeric substance through the monomer SP that constitutes polymkeric substance is 3.7cal at least ^0.5/ cm ^1.5Or littler polymkeric substance.And polymer B is, acid number is greater than 150mgKOH/g～200mgKOH/g, and the hydrogen bond item (δ h) that obtains polymkeric substance through the monomer SP that constitutes polymkeric substance is 1.5cal at least ^0.5/ cm ^1.5Or littler polymkeric substance.This hydrogen bond item (δ h) is the value that draws through the monomer institute inherent SP that constitutes this polymkeric substance.To introduce in the back this.

Can be not limited to above-mentioned polymer A and polymer B as the polymkeric substance of liquid compsn composition of the present invention.Promptly; When containing polymkeric substance in the liquid compsn that is forming image; The scuff resistance of the image that the usefulness China ink forms can reach the high-level scuff resistance of the object of the invention, and is then just passable with the polymkeric substance that specific modified siloxane compound is included in the said liquid compsn.Specifically, polymkeric substance can be to have: after liquid compsn is given recording medium, cause solid-liquid separation immediately, and on recording medium the polymkeric substance of fixed characteristic.In addition, adopt contain China ink simultaneously and contain polymkeric substance and the kinetic friction coefficient of the benchmark evaluation image that the liquid compsn of following specific modified siloxane compound forms 0.40 or lower getting final product.That is, so long as this liquid compsn remains in any polymkeric substance that forms the film with certain intensity on the recording medium after giving recording medium, all can be as the constituent of liquid compsn of the present invention.In addition, have this specific character, and to have the polymkeric substance that absorption is used to improve the specific modified siloxane compound characteristic that reaches the necessary following image smoothness of the object of the invention be most preferred.Here, the what is called among the present invention " benchmark evaluation image " means liquid compsn and pigment inks that employing contains polymkeric substance and specific modified siloxane compound simultaneously, adopts the image of the pigment inks of following condition.That is, relate to the condition that forms image: the emitted dose of every drop of liquid compsn is 3ng～5ng, resolution 1200dpi * 1200dpi, and 8-road bidirectional record and record load (recording duty) they are 50%.

The inventor is contained at least a polymkeric substance that is selected from polymer A with above-mentioned performance and polymerization B through other employing and is formed image with the liquid compsn of the modified siloxane compound of previous discussion with China ink, gets the scuff resistance of image with institute.The result finds, compares with the scuff resistance of the image that adopts the forms of liquid compositions that only contains the polymkeric substance with above-mentioned characteristic, and through using the modified siloxane compound, the image scuff resistance that can obtain forming is higher image significantly.

Therefore; The inventor adopts the aforesaid liquid compsn; Said composition not only contains the polymkeric substance with above-mentioned characteristic but also contain specific modified siloxane compound; Discovery can effectively reduce scuff resistance, and the image that uses China ink to form, to detect kinetic friction coefficient and the scuff resistance that has obtained image.The result finds that the kinetic friction coefficient of image is 0.40 or littler, therefore; Through adopting specific modified siloxane compound; Obtained the scuff resistance of image, and adopted the liquid compsn only contain above-mentioned performance polymer, compared significantly higher with the scuff resistance image of the image that adopts China ink to obtain.

Can obtain best formation of the present invention from above result, that is, liquid compsn had both contained at least a kind that is selected from above-mentioned polymer A and polymer B, and polymer A and B all have above-mentioned character, contain specific modified siloxane compound again.More specifically, use and to be selected from the polymer A with property and at least a polymkeric substance of polymer B.Polymer A is: acid number is 90mgKOH/g～150mgKOH/g, and the hydrogen bond item that obtains polymkeric substance through the monomer SP that constitutes polymkeric substance is 1.0cal ^0.5/ cm ^1.5～3.7cal ^0.5/ cm ^1.5Polymkeric substance.And polymer B is: acid number is greater than 150mgKOH/g～200mgKOH/g, and the hydrogen bond item that obtains polymkeric substance through the monomer SP that constitutes polymkeric substance is 1.0cal ^0.5/ cm ^1.5～1.5cal ^0.5/ cm ^1.5Polymkeric substance.Through adopting the liquid compsn of this formation, the modified siloxane compound may reside on the recording medium, and the result is the good scuff resistance that effect that the slipperiness that makes film coated surface that can obtain making the modified siloxane compound to be had improves is given full play to.Incidentally, set polymer A and polymer B and make that the lower limit by the hydrogen bond item (δ h) of the polymkeric substance of the monomeric SP acquisition that constitutes said polymkeric substance is 1.0cal ^0.5/ cm ^1.5Or bigger reason will be described below.

The inventor inquires into various modified siloxane compounds.The result finds, in order to realize the scuff resistance as the object of the invention, the modified siloxane compound of enumerating below the employing is necessary.Specifically, find to be selected from modified siloxane compound with following formula (1) expression, the modified siloxane compound of representing with following formula (2) and at least a kind of the modified siloxane compound represented with following formula (3) is more suitably.These modified siloxane compounds; When further also using with liquid compsn that contains polymkeric substance and pigment inks; When on the recording medium that for example has coating, forming image, adopting the kinetic friction coefficient of the benchmark evaluation image that above-mentioned TP obtains is 0.40 or lower.Incidentally, the kinetic friction coefficient of said benchmark evaluation image is the value that obtains according to aforesaid method.

Formula (1)

It is 8000～30000 that the modified siloxane compound of formula (1) expression has weight-average molecular weight.In the formula (1), R ₁The alkylidene group of expression carbonatoms 1～20, R ₂The alkyl of expression Wasserstoffatoms or carbonatoms 1～20, m representes 1～250, and n representes 1～100, and a representes 1～100, and b representes 0～100.

Formula (2)

The modified siloxane compound of formula (2) expression has weight-average molecular weight and is 8000～is lower than 50000.In the formula (2), R ₃The alkyl of representing Wasserstoffatoms or carbonatoms 1～20 respectively independently, R ₄Represent the alkylidene group of carbonatoms 1～20 respectively independently, p representes 1～450, and c representes 1～250, and d representes 0～100.

Formula (3)

The modified siloxane compound of formula (3) expression has weight-average molecular weight and is 8000～is lower than 50000, and HLB be 1～less than 7.In the formula (3), R ₅The alkyl of representing Wasserstoffatoms or carbonatoms 1～20 respectively independently, R ₆The alkylidene group of expression carbonatoms 1～20, q representes 1～100, and r representes 1～100, and e representes 1～100, and f representes 0～100.

The above results means, and makes the film coated surface slipperiness improve the modified siloxane compound of effect even have, and may not obtain best effect of the present invention sometimes.That is, adopt China ink and for example contain the weight-average molecular weight value when being in the liquid compsn formation image of above-mentioned extraneous modified siloxane compound, can not fully obtain the characteristic that the modified siloxane compound had originally sometimes.Its reason is still indeterminate, and the inventor infers as follows: as the mechanism that reaches the object of the invention, as stated, think due to the polymkeric substance adsorption of modification silicone compounds (or on the contrary too).Yet for example, when the modified siloxane compound with following formula (1) expression had weight-average molecular weight and surpasses 30000, because the influence of steric hindrance etc., polymkeric substance was difficult to take place to the absorption (or opposite) of modified siloxane compound.In addition, when the weight-average molecular weight with the modified siloxane compound of following formula (2) or following formula (3) expression be 50000 or more for a long time, because the influence of steric hindrance etc., polymkeric substance also is difficult to take place to the absorption (or opposite) of modified siloxane compound.The result can infer that this modified siloxane compound infiltrates into recording medium inside, and the kinetic friction coefficient of image does not often descend.On the other hand; When the modified siloxane compound of any one expression of following formula (1), following formula (2) and following formula (3) has weight-average molecular weight and is lower than 8000; Can infer that the modified siloxane compound that provides at imaging surface is very few, the kinetic friction coefficient of image does not often descend.Perhaps, when the weight-average molecular weight that has when said modified silane compound is lower than 8000, can infer that the modified siloxane compound itself infiltrates into recording medium inside, the scuff resistance of image does not often descend.

After this, with the hydrogen bond item (δ h) of explaining the polymkeric substance that the monomeric SP by constituting said polymkeric substance that adopted among the present invention obtains.At first, explain SP.SP receives the influence of functional group's kind in the said compound.SP is to confirm one of the solubleness of multiple compound or factor of said compound affinity to each other and when the SP of these compounds was similar each other, it is higher that their solubleness often becomes.SP can be categorized as the polarity item (δ p) of the dispersion force item that once departs from (δ d) that derives from electron distributions, the magnetism that gets free dipolar forces square generation or repulsive force and get free active hydrogen or the hydrogen bond item (δ h) of the hydrogen bond that lone-pair electron produce.In the present invention, the hydrogen bond item is applied to polymkeric substance and big because of the hydrogen bond item of polymkeric substance, so the affinity of polymkeric substance and water becomes stronger.The hydrogen bond item of polymkeric substance (δ h) can be confirmed through the monomeric SP that constitutes polymkeric substance.Then, can measure the hydrogen bond item (δ h) that obtains polymkeric substance through the monomeric SP that constitutes polymkeric substance through the total counting method of atomic group of Krevelen proposition; Wherein, With organic molecule as atomic group (referring to Krevelen, Properties of Polymer, the 2nd edition; New York, 154 (1976)).This method is described below.At first; By the dispersion force item Fdi of every mole of each atomic group in the relative organic molecule, the polar forces item Fpi and the hydrogen bond force item Fhi of every mole of each atomic group in the organic molecule relatively of every mole of each atomic group in the organic molecule relatively, confirm dispersion force item (δ d), polarity item (δ p) and the hydrogen bond item (δ h) of SP.Can be worth to confirm SP (δ) through using those that show in the following equation.

δd＝(∑Fdi)/V

δp＝(∑Fpi)/V

δh＝(∑Fhi)/V

δ＝(δd ²+δp ²+δh ²) ^1/2

(V is the molecular volume sum of atomic group)

The discovery that the inventor obtains is; For the polymkeric substance that contains in the liquid compsn; Can be through considering to judge that to the contributive hydrogen bond item of SP (δ) (δ h) this polymkeric substance infiltrates into recording medium inside with aqueous medium, or remain on the recording medium and fix.Indeterminate to contributive hydrogen bond item of SP (δ) (δ h) and polymkeric substance to the relation of the inner penetration degree of recording medium; But the inventor infers as follows: promptly; Hydrogen bond item (δ h) is from hydrogen bond, and big like the hydrogen bond item of polymkeric substance, then the affinity of polymkeric substance and water has the tendency that increases.Like liquid compsn of the present invention is the liquid compsn that mainly contains aqueous medium, so the hydrogen bond item of polymkeric substance strengthens, has polymer hydration, and the tendency of polymkeric substance coherency reduction each other.Can infer that be accompanied by this tendency, polymkeric substance does not condense on recording medium, be more prone to that residual polymer ratio has the tendency of reduction on recording medium to the recording medium internal penetration.

According to discovering of the inventor; Because its preferred range of polymkeric substance acid number is different; Polymer A and/or polymer B with hydrogen bond item value of the polymkeric substance that draws from the SP of following formation polymkeric substance are preferred as the constituent of liquid compsn.That is, to have acid number be 90mgKOH/g～150mgKOH/g polymkeric substance (polymer A) and have acid number between the polymkeric substance (polymer B) greater than 150mgKOH/g～200mgKOH/g in employing, and the preferable range of above-mentioned hydrogen bond item has following difference.When employing had the polymer A of above-mentioned scope acid number, hydrogen bond item (δ h) value that draws polymkeric substance from the SP that constitutes polymkeric substance can be preferably 1.0cal ^0.5/ cm ^1.5～3.7cal ^0.5/ cm ^1.5In addition, when adopting polymer B, hydrogen bond item (δ h) value that draws polymkeric substance from the SP that constitutes polymkeric substance can be preferably 1.0cal ^0.5/ cm ^1.5～1.5cal ^0.5/ cm ^1.5

Liquid compsn

Each components description that constitutes liquid compsn of the present invention is following.Liquid compsn of the present invention can be preferably colourless basically or slightly painted.Here, " colourless basically or slightly painted " refers to that image color does not reduce basically when liquid compsn is used to comprise the black imaging region of use.More particularly, it is preferred having no maximum absorbing wavelength at the visible region liquid compsn of 400nm～700nm.The liquid compsn that satisfies these conditions can be in vaporific a little.In addition, preferably be used for liquid compsn the image color of image and be not used for difference between the image color of image to liquid compsn being controlled at 0.3 or still less more preferably 0.1 or still less.For example, through in liquid compsn of the present invention, not comprising colorant, liquid compsn of the present invention can satisfy above-mentioned performance.

The silicone compounds of modification

The modified siloxane compound that is used for liquid compsn of the present invention is to be selected from by the modified siloxane compound of following formula (1) expression, by the modified siloxane compound of following formula (2) expression and at least a by in the modified siloxane compound of following formula (3) expression.

In these modified siloxane chemical combination by following formula (1), (2) and (3) expression, (C ₂H ₄O) and (C ₃H ₆O) difference representative ring oxirane unit and propylene oxide units.In each modified siloxane compound, ethylene oxide unit and propylene oxide units can random order such as random form or block form existence in the structure of compound.In the present invention, these unit preferably exist with random form or block form.It is to refer to ethylene oxide unit and propylene oxide units to arrange brokenly that these unit exist with random form.It is that the block that refers to each freer unit formation of each block and so formation is arranged regularly that these unit exist with block form.

The modified siloxane compound of formula (1) expression

Formula (1)

Here, the modified siloxane compound by formula (1) expression has 8000～30000 weight-average molecular weight; In formula (1), R ₁Be alkylidene group with 1～20 carbon atom, R ₂Be Wasserstoffatoms or the alkyl with 1～20 carbon atom, m is 1～250, and n is 1～100, a be 1～100 and b be 0～100.

R ₁The alkylidene group that preferably has 1～10 carbon atom in addition, particularly preferably is ethylidene, propylidene or butylidene.R ₂The alkyl that preferably has 1～10 carbon atom in addition, particularly preferably is ethyl or propyl group.Letter character m is preferred 1～250, and more preferably 1～100, be preferably 1～50 especially, letter character n is preferred 1～100, and more preferably 1～50.Letter character a is preferred 1～100, and more preferably 1～50.Letter character b is preferred 0～100, and more preferably 1～50.

The compound of above-mentioned formula (1) expression of adopting in the present invention is that the addition polymerization of two kinds of compounds representing through following formula obtains.That is, said compound is to be bonded to the ZGK 5 of n the Wasserstoffatoms on the Si and to have (one or more) ethylene oxide unit and/or (one or more) propylene oxide units and the addition polymerization between the compound that has the thiazolinyl structure on the compound end obtain through having n.Particularly, said compound is to obtain through the Wasserstoffatoms of ZGK 5 and the addition between the thiazolinyl.In following formula, m is 1-250, and n is 1-100, and a is 1-100, and b is that 0-100 and R are the thiazolinyls with 1-20 carbon atom.

The modified siloxane compound of formula (2) expression

Formula (2)

Here have 8000～be lower than 50000 weight-average molecular weight by the modified siloxane compound of formula (2) expression; In formula (2), R ₃Be respectively Wasserstoffatoms or alkyl independently with 1～20 carbon atom, R ₄Independently for having the alkylidene group of 1～20 carbon atom, p is 1～450 respectively, and each c is 1～250, and each d is 0～100.

R ₃Preferred respectively Wasserstoffatoms or have the alkyl of 1～10 carbon atom, more preferably Wasserstoffatoms, ethyl or propyl group.R ₄The alkylidene group that preferably has 1～10 carbon atom respectively, in addition, preferred especially ethylidene, propylidene or butylidene.Letter character p is preferred 1～450, and more preferably 1～100, preferred especially 1～50.

The compound of above-mentioned formula (2) expression of adopting in the present invention is that the addition polymerization of two kinds of compounds representing through following formula obtains.That is, said compound is to be bonded at the ZGK 5 of the Wasserstoffatoms on the Si on two ends and to have (one or more) ethylene oxide unit and/or (one or more) propylene oxide units and the addition polymerization between the compound of the structure that has thiazolinyl on the compound end obtain through having.Particularly, said compound is to obtain through the Wasserstoffatoms of ZGK 5 and the addition between the thiazolinyl.In following formula, p is 1-450, and c is 1-250, and d is that 0-100 and R are the thiazolinyls with 1-20 carbon atom.

The modified siloxane compound of formula (3) expression

Formula (3)

Here, have 8000～be lower than 50000 weight-average molecular weight by the modified siloxane compound of formula (3) expression and from 1～be lower than 7 HLB; In formula (3), R ₅Be respectively Wasserstoffatoms or alkyl independently with 1～20 carbon atom, R ₆For having the alkylidene group of 1～20 carbon atom, q is 1～100, and r is 1～100, e be 1～100 and f be 0～100.

R ₅Preferred separately Wasserstoffatoms or have the alkyl of 1～10 carbon atom, more preferably Wasserstoffatoms, ethyl or propyl group.R ₆The alkylidene group that preferably has 1～10 carbon atom separately, in addition, preferred especially ethylidene, propylidene or butylidene.Letter character e is preferably 1～100, and more preferably 1～50.Letter character f is preferably 1～100, and more preferably 1～50.

The compound of above-mentioned formula (3) expression of adopting in the present invention is that the addition polymerization of two kinds of compounds representing through following formula obtains.That is, said compound be through have be bonded to the ZGK 5 of the Wasserstoffatoms on the Si on two ends and have (one or more) ethylene oxide unit and/or (one or more) propylene oxide units and compound in the structure of the thiazolinyl on the compound end between addition polymerization obtain.Particularly, said compound is to obtain through the Wasserstoffatoms of ZGK 5 and the addition between the thiazolinyl.In following formula, q is 1-100, and r is 1-100, and e is 1-100, and f is that 0-100 and R are the thiazolinyls with 1-20 carbon atom.

As being selected from by at least a modified siloxane compound in the modified siloxane compound of above-mentioned formula (1), (2) and (3) expression, any compound can use, as long as can obtain to have the image according to the high-caliber scuff resistance of the object of the invention.Yet the research of being made by the inventor has disclosed the preferred especially modified siloxane compound with following weight-average molecular weight that uses.Specifically, under the situation of the modified siloxane compound of being represented by formula (1), the weight-average molecular weight that can preferably have (Mw) is 8000～30000, in addition, and preferred especially 8500～30000.Under situation by the modified siloxane compound of above-mentioned formula (2) or (3) expression, preferably have weight-average molecular weight (Mw) and be 8000～be lower than 50000, in addition, preferred especially 8500～30000.Here, weight-average molecular weight (Mw) is with regard to PS, presses the weight-average molecular weight of the MWD of GPC (GPC) measurement.Incidentally; Used modified siloxane compound among synthetic as stated the present invention; Because compound with (one or more) thiazolinyl and ZGK 5 as raw material are the mixtures with compound of molecular weight ranges, so the molecular weight of compound obtains with the molecular-weight average form.

The research of being made by the inventor discloses, and by the modified siloxane compound of above-mentioned formula (1) expression, it is (hydrophilic-lipophilic balance that preferred use has specific HLB; Value through the calculating of Griffin method) modified siloxane compound.More particularly, preferably has 1～11 HLB, more preferably 5～11 by the modified siloxane compound of above-mentioned formula (1) expression.

Here the modified siloxane compound by above-mentioned formula (1) expression is used for liquid compsn of the present invention; Set its weight-average molecular weight and also make its HLB in above-mentioned scope; When liquid compsn was used on the recording medium, the modified siloxane compound that infiltrates recording medium reduced.As a result, the modified siloxane compound by above-mentioned formula (1) expression is easy to be retained on the recording medium.Therefore, even the content of modified siloxane compound in liquid compsn by above-mentioned formula (1) expression is little here, but the kinetic friction coefficient that also can reduce effectively.The modified siloxane compound that satisfies above-mentioned condition and preferably can be used among the present invention by above-mentioned formula (1) expression comprises following: for example; FZ-2104; FZ-2130 and FZ-2191 (all these can obtain from DowCorning Toray Silicone ltd); KF-615A (can obtain) from chemical ltd of SHIN-ETSU HANTOTAI, TSF4452 (can obtain) from GE Toshiba Silicone ltd.Certainly, in the present invention, embodiment is not limited to these.

Here the modified siloxane compound by formula (2) expression is used for liquid compsn of the present invention; Set its weight-average molecular weight in above-mentioned scope; When being used for liquid compsn on the recording medium, the modified siloxane compound that infiltrates in the recording medium is reduced.As a result, the modified siloxane compound by above-mentioned formula (2) expression is easy to be retained on the recording medium.Therefore, even the content of modified siloxane compound in liquid combination by above-mentioned formula (2) expression is little, also can reduce the kinetic friction coefficient of image effectively here.The modified siloxane compound that satisfies above-mentioned condition and preferably can be used among the present invention by above-mentioned formula (2) expression can comprise: for example, and BYK333 (can obtain) by Byk Chemie Japan Co., Ltd..Certainly, in the present invention, embodiment never is limited to these.

The research of being made by the inventor discloses, and in the modified siloxane compound by above-mentioned formula (3) expression, it is (hydrophilic-lipophilic balance that preferred use has specific HLB; Value by the calculating of Griffin method) modified polyorganosiloxane compound.More particularly, must have 1～be lower than 7 HLB by the modified siloxane compound of above-mentioned formula (3) expression.

Here the modified siloxane compound by above-mentioned formula (3) expression is used for liquid compsn of the present invention; Set its weight-average molecular weight and also make its HLB in above-mentioned scope; When being used for liquid compsn on the recording medium, the modified siloxane compound that infiltrates recording medium is reduced.As a result, make modified siloxane compound be easy to be retained on the recording medium by above-mentioned formula (3) expression.Therefore, even the content of modified siloxane compound in liquid compsn of being represented by above-mentioned formula (3) is little, also can reduce the kinetic friction coefficient of image effectively.The modified siloxane compound by above-mentioned formula (3) expression that satisfies above-mentioned condition and preferably can be used among the present invention can comprise following: for example, and FZ-2203, FZ-2207, FZ-2222 and FZ-2231 (all these can both obtain from Dow Corning Toray Silicone ltd).Certainly, in the present invention, embodiment never is limited to these.

As previously mentioned, the weight-average molecular weight of modified siloxane compound (Mw) can be passed through GPC (GPC) measurement, and THF uses as moving phase.The measuring method that is used for the present invention is as follows.Measuring condition such as strainer, post, polystyrene standard sample and molecular weight thereof are not limited to following.

At first, put into the sample of measuring in the THF (THF) and keep static some hrs with dissolving preparation solution.Afterwards, (for example: trade(brand)name: TITAN 2 Syringe strainers, PTFE, 0.45 μ m with the anti-solvent membrane filter of hole dimension 0.45 μ m; Can obtain from SUN-SRi) filtering solution.Sample concentration in the sample solution will so be controlled so that make the content of modified siloxane compound can be at 0.1 quality %～0.5 quality %.

In GPC, use RI detector (diffraction efficiency detector).In order to measure the molecular weight in 1000 to 2000000 scopes exactly, preferably combination use a plurality of from the market available polystyrene gel post.For example, can make up and use four Shodex KF-806M (can obtain), perhaps use some suitable posts from Showa Denko K. K.Stable post in, again with the amount of about 0.1ml inject above-mentioned sample solution with the flow rate of 1ml/min in the heating chamber under 40 ℃ as the THF of mobile phase.

The weight-average molecular weight of the molecular weight calibration curved measurement sample of the polystyrene sample preparation through using standard.A kind of have about molecular weight calibration curve of 100～about 10000000 (for example, can obtain from Polymer Laboratories company) and can be used as polystyrene sample and use, and be fit to use at least about 10 kinds of polystyrene standard samples.

Based on the total mass of liquid compsn, the preferred 0.2 quality % of the modified siloxane compounds content (quality %) in the liquid compsn～5.0 quality %, more preferably 0.5 quality %～be lower than, 3.0 quality %.Especially, when the modified siloxane compound that uses by above-mentioned formula (2) expression, preferred 1.0 quality % of the modification silica ethane compounds content (quality %) in the liquid compsn～be lower than 3.0 quality %.Here the content of modified siloxane compound is 0.5 quality % or more, and the modified siloxane compound is retained on the recording medium so that the image with excellent especially scuff resistance to be provided satisfactorily.Yet here the content of modified siloxane compound is lower than 3.0 quality %, reduces to minimally because the caused defective of for example coking (kogation) is sprayed incidence, and this is preferred especially.

Polymkeric substance

As the polymkeric substance that is used for liquid compsn of the present invention, as previously mentioned, can use any polymkeric substance, as long as being liquid compsn, it is used for being retained in the polymkeric substance on the recording medium after the recording medium, be used for forming and reach the film of intensity to a certain degree.Yet; The research of being made by the inventor discloses; For the moistening phenomenon of jet hole that suppresses to produce owing to polymkeric substance; This phenomenon particularly can form problem when being used for ink-vapor recording to liquid compsn, optimum use respectively has at least a in polymer A and the polymer B of performance as previously mentioned.

The hydrogen bond item (δ h) that employed monomer SP through the formation polymkeric substance obtains polymkeric substance among the present invention is the value of trying to achieve by following mode.At first, obtain to constitute each monomeric hydrogen bond item (δ h) of polymkeric substance through inherent SP in each monomer that constitutes polymkeric substance.Then, each the monomeric composition (quality) that each monomeric hydrogen bond item (δ h) of the formation polymkeric substance that obtains multiply by constitute polymkeric substance is than (ratio of components when sum is defined as 1), to obtain each value.Next, amount to the hydrogen bond item (δ h) of trying to achieve polymkeric substance to the value that is obtained.

Have the acid number that is lower than 90mgKOH/g if constitute the polymkeric substance of liquid compsn of the present invention, this polymkeric substance can not be dissolved in the alkali, perhaps when the liquid compsn standing storage, can make polymkeric substance deposition occur.In addition; If polymkeric substance has the acid number that is lower than 90mgKOH/g; Add wherein and when so liquid compsn was by means of warm-type ink-jet recording system injection, it was difficult keeping stable injection character greatly with quantity at liquid compsn to the polymkeric substance of the scuff resistance that enough reaches the object of the invention.Therefore, preferably polymkeric substance has 90mgKOH/g or more acid number.On the other hand, if polymkeric substance has the acid number greater than 150mgKOH/g, then the water-bearing media that tends in being contained in liquid compsn of this polymkeric substance infiltrates in the recording medium, causes the high-level scuff resistance that can not obtain target of the present invention in some cases.Therefore, when polymkeric substance had the acid number greater than 150mgKOH/g, the hydrogen bond item (δ h) that preferably obtains polymkeric substance through the monomer SP that constitutes polymkeric substance was 1.5cal ^0.5/ cm ^1.5Or still less.Yet when polymkeric substance had the acid number greater than 200mgKOH/g, even controlled hydrogen bond item (δ h) by any way, in some cases, polymkeric substance can not be stayed on the recording medium with the quantity of the high-level scuff resistance that is enough to reach target of the present invention.Therefore, polymkeric substance preferably has 200mgKOH/g or acid number still less.

In addition, if the hydrogen bond item (δ h) that obtains polymkeric substance through the monomer SP that constitutes polymkeric substance is lower than 1.0cal ^0.5/ cm ^1.5The time, the polymer A or the polymer B that constitute liquid compsn of the present invention can cause the moistening phenomenon of jet hole owing to polymkeric substance significantly.As a result, for example, the curved flight meeting that drop occurs causes the damage of spraying character.Therefore, obtain the preferred 1.0cal of hydrogen bond item (δ h) of polymkeric substance through the monomer SP that constitutes polymer A or polymer B ^0.5/ cm ^1.5Or it is more.On the other hand, if the hydrogen bond item (δ h) that obtains polymkeric substance through the monomer SP that constitutes polymkeric substance greater than 3.7cal ^0.5/ cm ^1.5Even, controlled the acid number of polymkeric substance by any way, polymkeric substance also can infiltrate in the recording medium by the water-bearing media in being contained in liquid compsn.Therefore, can not obtain the scuff resistance of target of the present invention in some cases.

Summarizing these, is only for polymer A that is selected from formation liquid compsn of the present invention and at least a polymkeric substance in the polymer B, in order that the performance of acid number of being stipulated as follows and hydrogen bond item (δ h) combination.

Polymer A has the acid number of 90mgKOH/g～150mgKOH/g.In polymer A, except above-mentioned acid number characteristic, the hydrogen bond item (δ h) that obtains polymkeric substance through the monomer SP that constitutes polymkeric substance is 1.0cal ^0.5/ cm ^1.5～3.7cal ^0.5/ cm ^1.5In addition, in polymer A, the hydrogen bond item (δ h) that obtains polymkeric substance through the monomer SP that constitutes polymkeric substance is preferably 1.0cal ^0.5/ cm ^1.5～3.2cal ^0.5/ cm ^1.5Especially, in polymer A, obtain the further preferred 1.2cal of hydrogen bond item (δ h) of polymkeric substance through the monomer SP that constitutes polymkeric substance ^0.5/ cm ^1.5～1.8cal ^0.5/ cm ^1.5

On the other hand, polymer B has the acid number greater than 150mgKOH/g～200mgKOH/g.In polymer B, except above-mentioned acid number, the hydrogen bond item (δ h) that obtains polymkeric substance through the monomer SP that constitutes polymkeric substance is 1.0cal ^0.5/ cm ^1.5～1.5cal ^0.5/ cm ^1.5In addition, in polymer B, the hydrogen bond item (δ h) that obtains polymkeric substance through the monomer SP that constitutes polymkeric substance is preferably 1.2cal ^0.5/ cm ^1.5～1.5cal ^0.5/ cm ^1.5

As (one or more) monomer that is configured for the polymkeric substance in the liquid compsn of the present invention; Any monomer can use; As long as it can provide and have as the acid number of polymer performance and the polymkeric substance of hydrogen bond item (δ h); The hydrogen bond item of this polymkeric substance is to obtain through the monomer SP that constitutes this polymkeric substance, as stated.Specifically, any monomer cited below can use as the monomer that constitutes polymkeric substance.

Vinylbenzene, and alpha-methyl styrene; The just own ester of ethyl propenoate, n-butyl acrylate, vinylformic acid, TEB 3K and benzyl methacrylate; Monomer with carboxyl is like vinylformic acid, methylacrylic acid, Ba Dousuan, ethylacrylic acid, propyl group vinylformic acid, isopropylacrylic acid, methylene-succinic acid and fumaric acid; Has sulfonic monomer, like styrene sulfonic acid, sulfonic acid-2-propyl group acrylic amide, vinylformic acid-2-sulfonic acid ethyl ester, methylacrylic acid-2-sulfonic acid ethyl ester and butyl acrylic amide sulfonic acid; And the monomer with phosphonate group, like methylacrylic acid-2-phosphinic acid ethyl ester and vinylformic acid-2-phosphinic acid ethyl ester.

In the present invention, under the situation of using polymer A, in the above-mentioned monomer of enumerating, preferably contain at least a monomer that is selected from vinylbenzene, n-butyl acrylate and benzyl methacrylate.In addition, the monomer that constitutes polymer A preferably has two kinds of vinylbenzene and n-butyl acrylates.In constituting the monomer of polymer A, the mass ratio of n-butyl acrylate and vinylbenzene (n-butyl acrylate/vinylbenzene) is preferably greater than 0.2 especially～is lower than 0.35.Under the situation of using polymer B, in the above-mentioned monomer of enumerating, preferably contain at least a monomer that is selected from vinylbenzene and alpha-methyl styrene.In addition, the monomer that constitutes polymer B preferably has two kinds of vinylbenzene and alpha-methyl styrenes.In constituting the monomer of polymer B, the mass ratio preferred especially 0.90 of alpha-methyl styrene and vinylbenzene (alpha-methyl styrene/vinylbenzene) or still less.In the present invention, not too hope to use monomer, like oxyethane, because the film toughness that on recording medium, forms possibly diminish with non-ionic group.

Polymkeric substance (be selected from polymer A and the polymer B at least a) preferably has 5000～15000 weight-average molecular weight, and best is 6000～9000.Have the polymkeric substance of the weight-average molecular weight in the above-mentioned scope, after liquid compsn is used on the recording medium, be easy to be retained on the recording medium, be not subject to the sterically hindered influence in addition.Therefore, polymkeric substance is easy to absorb the modified siloxane compound, to such an extent as to can reduce the kinetic friction coefficient of image effectively.

Based on the total mass of liquid compsn, the polymkeric substance in the liquid compsn (being selected from least a polymkeric substance in polymer A and the polymer B) preferably its content (quality %) is 0.5 quality %～5.0 quality %, and that best is 2.5 quality %～4.0 quality %.Because the content of polymkeric substance is in above-mentioned scope, so polymkeric substance can be retained on the recording medium with the gratifying quantity of the scuff resistance of image.In addition, because the content of polymkeric substance is in above-mentioned scope,, be difficult for being caused like the curved flight of drop so, spray the destruction of character because the moistening phenomenon of jet hole that polymkeric substance produces can be suppressed.

Water-bearing media

In liquid compsn of the present invention, the water-bearing media of use can be the mixed solvent of water or water and water-miscible organic solvent.Based on the total mass of liquid compsn, preferred its content (quality %) of the water-miscible organic solvent in the liquid compsn is 3.0 quality %～50.0 quality %.

Water-soluble solvent there is not special limitation, as long as it is water miscible.Like any can the use separately among following cited those, also can two kinds or more kinds of combination use.Specifically, following water-miscible organic solvent can use, for example, and alkanediol class such as 1,3 butylene glycol, 1,5-pentanediol, 1,2-pinakon and 1,6-pinakon; Gylcol ether such as glycol ether monomethyl (or ethyl) ether and triglycol one ethyl (or butyl) ether; Alkyl alcohols with 1～4 carbon atom is like ethanol, Virahol, n-butanols, isopropylcarbinol, sec-butyl alcohol and the trimethyl carbinol; Carboxylic acyloxy amine such as N, dinethylformamide and DMAC N,N; Ketone or ketols such as acetone, methyl ethyl ketone and 2-methyl-2-hydroxyl penta-4-ketone; Cyclic ethers class such as THF and two

alkane; Glycerine; Glycols is like-terepthaloyl moietie, glycol ether, triglycol and Tetraglycol 99; Polyoxyethylene glycol with 200～1000 average molecular weights, as 1,2-or 1, ammediol and 1,2-or 1,4-butyleneglycol; Di-alcohols such as sulfo-glycol, 1,2,6-hexanetriol and acetylenediol verivate; Heterocyclic such as 2-Pyrrolidone, N-N-methyl-2-2-pyrrolidone N-, 1,3-dimethyl--2-imidazolone and N-methylmorpholine; And sulfocompound, like DMSO 99.8MIN..

As water, preferably use deionized water (ion-exchanged water).The preferred 50.0 quality % of water-content in the liquid compsn (quality %)～95.0 quality % are based on the total mass of liquid compsn.

Other composition

Except that mentioned component, liquid compsn of the present invention can contain preserve moisture solid matter such as urea, urea derivatives, TriMethylolPropane(TMP) or trimethylolethane.The preferred 0.1 quality % of the solid matter content of preserving moisture (quality %) in the liquid compsn～20.0 quality %, that best is 3.0 quality %～10.0 quality %, based on the total mass of liquid combination.

In order to cause that liquid compsn has any physical properties on demand, liquid compsn further contains various additives such as pH regulator agent, rust-preventive agent, sanitas, mould inhibitor, inhibitor and anti-reducing agent.

Pigment inks

In imaging process, use the one-tenth of forming pigment inks to grade with describing below with the invention described above liquid compsn.

Pigment

In China ink, might use the pigment of the polymer dispersion (polymer dispersion pigment) of dispersion agent dispersed color, and self-pigment of decentralized (self-decentralized pigment), in this pigment, introduced hydrophilic radical the surface portion of pigment particles.Possibly use pigment in addition with organic group; This organic group contains and the polymkeric substance of pigment particles surface chemistry bonding (polymer-bonded self decentralized pigment); And the dispersed microcapsule-type pigment that has been modified, so that give their dispersions and need not use any dispersion agent.Certainly, these different pigment of dispersing mode can make up use.The preferred 0.1 quality % of the content of pigment (quality %)～15.0 quality % in the China ink.Based on the total mass of China ink, that best is 1.0 quality %～10.0 quality %.

As the pigment that is used for black ink, preferably use carbon black such as furnace treated black, dim, acetylene black or thermally oxidized black.Specifically, following from the market available product can use, for example:

RAVEN:1170,1190 ULTRA-II, 1200,1250,1255,1500,2000,3500,5000 ULTRA, 5250,5750 and 700 (all these can be obtained by ColumbianCarbon Japan ltd); BLACK PEARLS L, REGAL:330R, 400R and 660R, MOGUL L, MONARCH:700,800,880,900,1000,1100,1300,1400 and 2000 and VALCAN XC-72 (all these can obtain from Cabot company); COLOR BLACK:FW1, FW2, FW2V, FW18, FW200, S150, S160 and S170, PRINTEX:35, U, V, 140U and 140V, SPECIAL BLACK:6,5,4A and 4 (all these can obtain from Degussa company); And No.25, No.33, No.40, No.47, No.52, No.900, No.2300, MCF-88, MA600, MA7, MA8 and MA100 (all these can obtain from Mitsubishi Chemical ltd).

Recently the carbon black of preparation also can use.Certainly, in the present invention, embodiment never is limited to this, and any habitual known carbon black can use.To not restriction of carbon black, the black pigment that also can be used as of the thin magneticsubstance particle of magnetite, ferrite or its analogue and titanium uses.

In color ink, use pigment dyestuff as pigment optimization.Specifically, following can use, for example:

Water-insoluble azo pigment such as toluidine red, toluidine maroon, hansa yellow, diarylide yellow and pyrazolone red; Water-soluble azo pigment such as lithol red, daylight are purplish red, lithol fast scarlet nrh and permanent red 2B; From the verivate of vat dyes, like alizarin, indanthrone and thioindigoid maroons; Phthalocyanine type pigment such as phthalocyanine blue and phthalocyanine green; Quinacridone type pigment such as quinacridone are red pinkish red with quinacridone; Perylene type pigment such as perylene Hong are with perylene scarlet; Yellow and the isoindolinone orange of isoindolinone type pigment such as isoindolinone; Imidazolone type pigment such as benzimidazolone are yellow, benzimidazolone is orange and benzimidazolone is red; Red and the pyranthrone orange of pyranthrone type dye such as pyranthrone; Indigo type pigment, condensation azo type pigment, thioindigo type pigment; Diketopyrrolopyrrolecocrystals type pigment, flavanthrone is yellow, amido yellow; Quinophthalone is yellow; The nickel azophosphine, the copper azomethine is yellow, purple cyclic ketones orange (PerinoneOrenge); Anthrone orange, join (two) anthracene ester red with two

the piperazine purple.Certainly, in the present invention, embodiment never is limited to this.

When organic pigment shows with color index (C.I.) number numerical table; 12,13,14,17,20,24,74,83,86,93,97,109,110,117,120,125,128,137,138,147,148,150,151,153,154,166,168,180,185 following can the use, for example: the C.I. Pigment Yellow 73:, etc.; C.I. pigment orange; 16,36,43,51,55,59,61,71, etc.; C.I. Pigment red; 9,48,49,52,53,57,97,122,123,149,168,175,176,177,180,192,215,216,217,220,223,224,226,227,228,238,240,254,255,272, etc.; 19,23,29,30,37,40,50 C.I. pigment violet:, etc.; C.I. Pigment blue: 15,15:1,15:3,15:4,15:6,22,60,64, etc.; C.I. Pigment green; 7,36, etc.; With the C.I. pigment brown: 23,25,26, etc.Certainly, in the present invention, embodiment never is limited to this.

Polymkeric substance

Polymkeric substance can be used in the China ink.As polymkeric substance, can be used as the dispersion agent of colo(u)rant dispersion in water-bearing media used, or it is added in the China ink separately.As the polymkeric substance that is used for here, any polymkeric substance can use.But, in order to reach the scuff resistance of target of the present invention, the preferred polymkeric substance that uses with the performance that is described below.That is to say, preferably be used for the polymkeric substance of liquid compsn of the present invention, that is, after liquid compsn is used for recording medium, can remain in the polymkeric substance on the recording medium, be used for forming film with certain intensity.In addition, be combined under the situation of combination use, especially preferably be used in the polymkeric substance homogenizing in these liquid compsns and the China ink at liquid compsn and China ink.Especially, the polymkeric substance that is preferred in the liquid compsn is same polymkeric substance with the polymkeric substance that is used for China ink, that is, polymkeric substance has same performance (same acid number and obtain the hydrogen bond item (δ h) of polymkeric substance through the monomer SP that constitutes polymkeric substance).In this case, the polymkeric substance that is used for China ink can have with the polymer phase that is used for the invention described above liquid compsn with performance.

The monomer of formation polymkeric substance specifically can comprise following, constitutes at least two kinds of monomers of polymkeric substance.Here, at least a preferably hydrophilic monomer in them.Monomer can comprise vinylbenzene, vinyl naphthalene, aliphatic alcohol esters, vinylformic acid, toxilic acid, methylene-succinic acid, fumaric acid, vinyl-acetic ester, vinyl pyrrolidone, acrylic amide and the verivate thereof of α β-ethylenic unsaturated carboxylic acid.At least a preferably hydrophilic monomer in the monomer of formation polymkeric substance.As the form of polymkeric substance, can comprise segmented copolymer, random copolymers, graft copolymer or salt or any analogue in these.In addition, natural polymer (resin) also can use like rosin, lac and starch.These polymkeric substance are soluble in the aqueous solution that has dissolved alkali, and are the polymkeric substance of caustic solubility type.

The preferred 0.5 quality % of polymer content in the China ink (quality %)～5.0 quality % is based on the total mass of China ink.Polymkeric substance also preferably has 1000～15000 weight-average molecular weight.In addition, polymkeric substance preferably has the acid number of 90mgKOH/g～200mgKOH/g.

Water-bearing media

In China ink, can use water-bearing media, this water-bearing media is the mixed solvent of water or water and water-miscible organic solvent.The preferred 3.0 quality % of water-miscible organic solvent content (quality %) in the China ink～50.0 quality % are based on the total mass of China ink.

There is not special limitation for water-miscible organic solvent, as long as it is water miscible.As any can the use separately in following cited those, also can two kinds or more kinds of being used in combination.Specifically, below water-miscible organic solvent can use, for example, alkanediol class such as 1,3 butylene glycol, 1,5-pentanediol, 1,2-pinakon and 1,6-pinakon; Gylcol ether such as glycol ether monomethyl (or ethyl) ether and triglycol one ethyl (or butyl) ether; Alkyl alcohols with 1～4 carbon atom is like ethanol, Virahol, n-butanols, isopropylcarbinol, sec-butyl alcohol and the trimethyl carbinol; Carboxylic acyloxy amine such as N, dinethylformamide and DMAC N,N; Ketone or ketols such as acetone, methyl ethyl ketone and 2-methyl-2-hydroxyl penta-4-ketone; Cyclic ethers class such as THF and two

alkane; Glycerine; Glycols such as terepthaloyl moietie, glycol ether, triglycol and Tetraglycol 99; Glycols is as 1,2-or 1, ammediol, 1,2-or 1,4-butyleneglycol, polyoxyethylene glycol, thiodiglycol, 1,2,6-hexanetriol and acetylenediol (acetylene glycol) verivate; Heterocyclic such as 2-Pyrrolidone, N-N-methyl-2-2-pyrrolidone N-, 1,3-dimethyl--2-imidazolone and N-methylmorpholine; And sulfocompound, like METHYL SULFONYL METHANE..

As water, preferably use deionized water (ion-exchanged water).The preferred 50.0 quality % of water-content in the China ink (quality %)～95.0 quality % are based on the total mass of China ink.

Other composition

Except that mentioned component, China ink can contain preserve moisture solid matter such as urea, urea derivatives, TriMethylolPropane(TMP) or trimethylolethane.The preferred 0.1 quality % of the solid matter content of preserving moisture (quality %) in the China ink～20.0 quality %, that best is 3.0 quality %～10.0 quality %, based on the total mass of China ink.

In order to make China ink have the physical properties of any preset value according to circumstances, China ink further contains various additives such as pH regulator agent, rust-preventive agent, sanitas, mould inhibitor, inhibitor and reduction prevent agent.

The cover group of liquid compsn and China ink

Liquid compsn of the present invention can combine with China ink to use with the form of the liquid compsn and the cover group of China ink

Image forming method

Image forming method of the present invention be characterised in that have (i) liquid compsn be applied to the step of recording medium and (ii) pigment inks be applied to the step of recording medium.Especially, step (i) with (ii) preferably so carry out so that liquid compsn is contacted on recording medium with pigment inks each other.This composition that relies on invention, the imaging scuff resistance of use China ink can reach high-caliber good scuff resistance, even to such an extent as under with so strong pressure, scratch image at its non-recording areas scuffing recording medium, but colorant also is difficult to wipe.

When liquid compsn and pigment inks are used on the recording medium, carry out through the combination of for example following method or these methods.Specifically, effectively (a) the method for using of China ink behind the applicating liquid compsn with (b) using pigment inks after the application process of liquid compsn.In the present invention, any method in these methods all can suitably be selected.Yet, consider to the objective of the invention is to obtain the image that ordinary method can't obtain preferred method of use (b) with high-level excellent scuff resistance.Under these circumstances, the timed interval of applicating liquid compsn does not have special limitation afterwards for using China ink.Yet,, use these timed intervals and preferably so confirm so that China ink and liquid compsn are contacted with each other under liquid state and mix for pigment and the bonding force between the polymkeric substance in the liquid compsn in China ink of improved action more.

Amount as for being used in the liquid compsn on the recording medium does not have special limitation, as long as can obtain effect of the present invention.Yet, consider to make the less appearance of any foaming (beading) and aspect fixed speed, improve that so it measures preferred 20 quality %～50 quality %, more preferably 25 quality %～50 quality % are based on the amount of used China ink.Here, " foaming " relate to following illustrated phenomenon.The phenomenon that relates to is: keep flowable state before China ink is completely fixed on recording medium; Some points of forming of China ink move on the surface of in-plane at recording medium brokenly in this state, other adjacent drop add this move and can form aggregate cause the inhomogeneous of image color.

If when liquid compsn is only used, very big difference is arranged on the recording medium of its image-region at the imaging region and the scuff resistance that can not occur between the imaging region.Therefore, be preferred especially for being applied to liquid compsn in the zone and the zone wider that comprise image than this zone.Yet, when liquid compsn is used with the above-mentioned amount of 2G quality %～50 quality %, for being applied to liquid compsn in the zone that comprises image and also extensively being difficult than this zone.Here, in general, have big capillary liquid and having little capillary liquid when contacting with each other, having big capillary liquid and can orientedly have the characteristic that little capillary liquid moves.Therefore, in order to be used to liquid compsn to comprise the zone and the zone wider than these zones of image, the amount of setting liquid compsn is preferred 20%～50%, and more preferably 25%～50%, based on the quantity of used China ink, it is described preferably to carry out the back.That is to say, preferably set liquid compsn and have the high surface tension of China ink.When China ink has contacted with liquid compsn each other, set the whole zone that liquid compsn can make this liquid compsn be diffused into and be applied to above, China ink by this way.

In the method for formation image of the present invention, do not limit especially that China ink or liquid compsn are administered to the method on the recording medium, but particularly preferably be not only China ink but also liquid compsn all can be administered on the recording medium through ink jet method.This is to be easy to control as stated because liquid compsn is easy to be applied to exactly the amount of image-region and liquid compsn to be used.The China ink of using through ink jet method and the amount of liquid compsn can be controlled through survey record load etc. rightly.

Ink jet recording method

Liquid compsn of the present invention be particularly preferred for China ink and liquid compsn by ink-jet systems eject with so be recorded in the ink jet recording method on the recording medium.Ink jet recording method can comprise, for example, a kind of recording method be make mechanical energy act on China ink with liquid compsn so that ejecting ink and liquid compsn, and another kind of recording method be make heat energy act on black and liquid compsn so that ejecting ink and liquid compsn.Especially, liquid compsn of the present invention is preferred for using in the recording method of heat energy.

Print cartridge

Print cartridge of the present invention has the liquid compsn storage compartment of store liquid therein compsn, and is characterised in that the liquid compsn that is stored in the liquid compsn storage compartment is an aforesaid liquid compsn of the present invention.

Record cell

Record cell of the present invention is equipped with the liquid compsn storage compartment of store liquid therein compsn and the record-header of atomizing of liquids compsn therefrom, and the liquid compsn that it is characterized in that being stored in the liquid compsn storage compartment is an aforesaid liquid compsn of the present invention.Especially, preferably such record cell, wherein record-header acts on therefrom atomizing of liquids compsn of liquid compsn through making heat energy.

Ink-jet recording device

Ink-jet recording device of the present invention is equipped with the liquid compsn storage compartment of store liquid therein compsn and the record-header of atomizing of liquids compsn therefrom, and the liquid compsn that it is characterized in that being stored in the liquid compsn storage compartment is an aforesaid liquid compsn of the present invention.Especially, preferably such ink-jet recording device, wherein record-header acts on therefrom atomizing of liquids compsn of liquid compsn through making heat energy.

The embodiment of ink-jet recording device explains as follows.At first, the constructed embodiment of record-header is shown in Fig. 2 and 3, and this record-header is the major parts that utilizes the ink-jet recording device of heat energy, and Fig. 2 is the cross-sectional view of record-header 13 along its ink passage, and Fig. 3 is the cross-sectional view along Fig. 2 middle conductor 3-3.Record-header 13 comprises the member and the heating unit substrate component 15 of (nozzle) 14 that have ink passage.Heating unit substrate component 15 comprises resist 16, electrode 17-1 and 17-2, thermoresistance layer 18, heat is held layer 19 and substrate 20.

When the electrical signal of impulse form put on electrode 17-1 and the 17-2 of record-header 13, heat produced in the zone of being represented by the n in the heating unit substrate component 15 sharp so that with China ink 21 that this surface, district contacts in produce bubble.The pressure of bubble is released meniscus 23 and China ink 21 sprays with the form of ink droplet 24 from the jet holes 22 of nozzle 14 and flies to recording medium 25.

Fig. 4 illustrates the external device (ED) of many record-headers embodiment, the arrangement all as shown in Figure 2 of each record-header in wherein many record-headers.Many record-headers comprise the sheet glass 27 with multi-nozzle 26, with the similar record-header shown in Fig. 2.

Fig. 5 is a skeleton view of representing to add jet recording device embodiment.Flap 61 is Wiping members, and the other end is cantilevered to the one of which end by flap-protection member maintenance.Flap 61 is installed in the zone of carrying out record position near record-header 65, and is held with the form of the stroke that stretches into 65 processes of record-header.

The lid of the jet hole face of Reference numeral 62 expression record-headers 65 is configured on the starting position near flap 61, and so installs so that it moves along the direction perpendicular to record-header 65 travel directions, and contacts the completion capping with the jet hole face.The black resorber of Reference numeral 63 expressions closes on flap 61 and installs, and, be similar to flap 61, be held by this way so that stretch into the stroke that record-header 65 moves.Spraying recovery assembly 64 is made up of flap 61, lid 62 and black resorber 63.Flap 61 dewaters and dust from the jet hole face with black resorber 63.

Reference numeral 65 expressions have the record-header of injection ability generating unit and are ejected into China ink setting and are equipped with on the jet hole face recording medium in opposite directions of jet hole, accomplish record.The balladeur train that Reference numeral 66 expressions are equipped with record-header 65 is so that record-header 65 can move.Balladeur train 66 combines with the axis of guide 67 slidably.The part of balladeur train 66 is connected (not shown) with the belt 69 that drives through motor 68.Like this, balladeur train 66 can move and makes record-header 65 move to the zone of closing on therewith from posting field along the axis of guide 67.

The paper feeding part of recording medium is inserted in Reference numeral 51 expressions, and Reference numeral 52 expressions drive the paper-feed roll (not shown) by motor.Under so forming, recording medium is admitted to the jet hole face place in opposite directions with record-header 65, and with the carrying out of writing down, is discharged by the paper transport portion with paper conveying roller 53.Spraying the lid 62 of recovery component 64 when record-header 65 returns its starting position after record is accomplished returns from the shift motion of record-header 65.Like this, the jet hole face of wiping record-header 65.

When lid 62 contacts with the jet hole face of record-header 65 when carrying out capping, lid 62 moves so that stretch into the shift motion of record-header by this way.When record-header 65 when its starting position moves to the position of opening entry, lid 62 is placed on the position identical with the above-mentioned position of wiping jet hole face with flap 61.As a result, the jet hole face of record-header 65 when mobile also by wiping.Record-header moves to its starting position and not only accomplishes record or spraying when recovering and carry out; And record-header carries out in order to write down when also in posting field, moving; Record-header moves near on the starting position with each posting field of appointed interval in the process of record, and the jet hole face is wiping when mobile also.

Fig. 6 is that expression stores the figure of embodiment of print cartridge 45 that sends into the China ink of record-header through ink supply member (for example pipeline).Here, the black storage compartment of Reference numeral 40 expressions, for example the China ink bag has stored therein and has supplied with China ink.The stopper 42 of rubber system is equipped with at its top.The spicule (not shown) can insert in this stopper 42 so that the China ink in the China ink bag 40 can be fed in the magnetic head.The resorber of useless China ink is accepted in Reference numeral 44 expressions.

In the present invention, be not limited to the record cell that wherein record-header and print cartridge separate, a kind of equipment also is preferred for the equipment processed by integral body shown in Figure 7.In Fig. 7, Reference numeral 70 expression record cells store in the interval of the for example black storage resorber of the black storage compartment that stores China ink, are spraying from having the porous record-header of being permitted 71 with the form of black drop with the China ink in the so black resorber.Replace black resorber, record cell is so to install so that black storage compartment becomes the China ink bag that spring or analogue internally are housed.Reference numeral 72 is represented air passages openings, makes the inside and the atmosphere of print cartridge through this opening.This record cell 70 is used to replace record-header shown in Figure 5 65, and is releasably attached on the balladeur train 66.

Next step utilizes description the ink-jet recording device of mechanical energy.This device is characterised in that to have the record-header that assembling has the formation nozzle plate of many nozzles; Pressure-generating device comprises piezoelectric dielectric material and electro-conductive material; With around being full of China ink around the pressure-generating device, and in pressure-generating device, make pressure-generating device distortion from jet droplets by applying voltage.

Fig. 8 is the embodiment synoptic diagram of this recording head structure of expression.Record-header is by the ink passage 80, the orifice plate 81 that are communicated with black chamber (not shown) and makes pressure directly act on the oscillating plate 82 of China ink, the piezo-electric device 83 that is connected with this oscillating plate 82 and according to the electrical signal distortion, and substrate 84 compositions that are used to support and reinforce orifice plate 81 and oscillating plate 82.Make the oscillating plate distortion that is connected with piezo-electric device 83 through giving the deformation stress that piezo-electric device 83 produces with pulsed voltage, therefore cause of jet hole 85 injections of black drop from orifice plate 81 for exerting pressure to the black inside of ink passage 80.This record-header can use at the state of having organized into same ink-jet recording device as shown in Figure 5.

Liquid compsn of the present invention can be used in the above-mentioned ink-jet recording device, and when reading relevant specification sheets, term " China ink " quilt " liquid compsn " replaces.That is to say that print cartridge of the present invention is the print cartridge with liquid compsn storage compartment of store liquid therein compsn, liquid compsn of the present invention here can be used as the liquid compsn that is stored in the liquid compsn storage compartment and uses.Record cell of the present invention can be to have the liquid compsn storage compartment of store liquid therein compsn and the record cell of the record-header of atomizing of liquids compsn therefrom, and liquid compsn of the present invention here uses as the liquid compsn in the storing liquid composition stores part.Ink-jet recording device of the present invention can be to have the liquid compsn storage compartment of store liquid therein compsn and the jet recording device that liquid compsn therefrom sprays, and liquid compsn of the present invention here can be used as the liquid compsn that is stored in the liquid compsn storage compartment and uses.

Embodiment

The present invention is explained by the embodiment that provides, Comparative Examples and reference example with more details below.Only if the present invention never is limited to the following example and surpasses its purport.Following, " part " or " % " is only if having special indication by quality.

The preparation of aqueous solutions of polymers

For each polymkeric substance (weight-average molecular weight of each polymkeric substance is shown in Table 1) in the polymkeric substance 1～28 that obtains by monomer copolymerization that is shown in Table 1; Add ion-exchanged water with preparation aqueous solutions of polymers 1～28, wherein various polymkeric substance are the solid substance concentration of 10 quality %.For each polymkeric substance, multipolymer uses with the potassium hydroxide aqueous solution neutralization of 10 quality % and as polymkeric substance.In table 1, monomeric abbreviation is following.

Table is annotated: St: vinylbenzene

α-MSt: alpha-methyl styrene

BZMA: benzyl methacrylate

NBA: n-butyl acrylate

MMA: TEB 3K

MA: methacrylic ester

AA: vinylformic acid

Table 1: the salient features of aqueous solutions of polymers 1～28

Obtain the hydrogen bond item (δ h) of polymkeric substance through the monomer SP that constitutes polymkeric substance:

Obtain obtaining the hydrogen bond item (δ h) of polymkeric substance through the monomer SP that constitutes polymkeric substance by following mode.At first, obtain to constitute each monomeric hydrogen bond item (δ h) of polymkeric substance through intrinsic solubility parameter in each monomer that constitutes subject polymer.Secondly, make each monomeric composition (quality) that each the monomeric hydrogen bond item (δ h) that passes through the formation polymkeric substance that as above obtains multiply by the formation polymkeric substance obtain each value than (ratio of components when the sum total is defined as 1).Then, amount to the hydrogen bond item (δ h) that obtains obtaining polymkeric substance to the value that is obtained through the monomer SP that constitutes polymkeric substance.With regard to the various polymkeric substance that are used to prepare aqueous solutions of polymers, obtain every kind of monomeric hydrogen bond item (δ h) through the every kind of monomer inherent SP that constitutes polymkeric substance and be shown in Table 2.

Take polymkeric substance 1 as embodiment; It is vinylbenzene, methyl acrylate and the vinylformic acid multipolymer of (forming (quality) than=28: 58: 14), will explain the hydrogen bond item (δ h) that how to obtain obtaining through the monomer SP that constitutes polymkeric substance polymkeric substance below particularly.As under tabulate 2 visiblely, (its unit is cal to obtain the hydrogen bond item through vinylbenzene, methyl acrylate and the acrylic acid SP that constitutes polymkeric substance 1 ^0.5/ cm ^1.5) be respectively 0.00,3.93 and 5.81.Therefore, obtain obtaining the hydrogen bond item (δ h) of polymkeric substance 1, as through shown in the following expression by the monomer SP that constitutes polymkeric substance 1.

Obtain hydrogen bond item (the δ h)=0.00 * 0.28+3.93 * 0.58+5.81 * 0.14=3.09cal of polymkeric substance through the monomer SP that constitutes polymkeric substance ^0.5/ cm ^1.5

Table 2: each monomeric hydrogen bond item

* 1: hydrogen bond item (δ h) obtains through the water-soluble parameter of each monomer inherent

With regard to the polymkeric substance in the aqueous solutions of polymers of preparation in advance, hydrogen bond item (δ h) value that obtains polymkeric substance through the monomer SP that constitutes polymkeric substance is shown in Table 3.The acid number of each polymkeric substance and the value of weight-average molecular weight also are shown in Table 3.In addition, table 3 is illustrated in as monomer and respectively has n-butyl acrylate or alpha-methyl styrene in the polymkeric substance of vinylbenzene and n-butyl acrylate or vinylbenzene and alpha-methyl styrene to the value of cinnamic mass ratio.

Table 3

Polymer performance in aqueous solutions of polymers

* 1: the hydrogen bond item of polymkeric substance (δ h) obtains through the water solubility of monomer parameter that constitutes polymkeric substance

* 2: positive butyl ester of the propylene in the polymkeric substance and cinnamic mass ratio

* 3: alpha-methyl styrene in the polymkeric substance and poly mass ratio

The preparation of pigment dispersion

The preparation of pigment dispersion 1

10 parts of pigment, 5 parts of polymkeric substance 11 that obtained by monomer copolymerization that are shown in Table 1 mix with ion-exchanged water of 85 parts, follow by levigate 3 hours of vertical grinding machine in batches, prepare pigment dispersion 1.Here, C.I. pigment Blue 15: 3 use as pigment.As polymkeric substance 11, multipolymer uses with the potassium hydroxide aqueous solution neutralization of 10 quality % and as polymkeric substance.Make of strainer (trade(brand)name: HD CII can from the Nihon Pall ltd obtain) pressure filtration of the dispersion-s of acquisition like this through 2.5 μ m hole dimensions.Add water has pigment concentration and the 5 quality % of 10 quality % with preparation the pigment dispersion 1 of polymer concentration toward this dispersion-s.

The preparation of pigment dispersion 2

By preparing the pigment dispersion 2 of the polymer concentration of pigment concentration with 10 quality % and 5 quality %, except the polymkeric substance 13 that is obtained by monomer copolymerization that is shown in Table 1 replaces polymkeric substance 11 use with pigment dispersion 1 identical mode.

The preparation of pigment dispersion 3

By preparing the pigment dispersion 3 of the polymer concentration of pigment concentration with 10 quality % and 5 quality %, except the polymkeric substance 18 that is obtained by monomer copolymerization that is shown in Table 1 replaces polymkeric substance 11 use with pigment dispersion 1 identical mode.

Synthesizing of modified siloxane compound

The modified siloxane compound, compound 1～12 is according to following synthetic embodiment synthetic.

Compound 1

Use glass and TM is housed and the container of whipping appts, synthetic compound 1 in the following manner.In this container, under the situation of platinum catalyst, synthesize compound 1 as main ingredient through addition reaction by the polysiloxane compound of following formula (A) expression with by the polyoxyethylene compound that following formula (B) is represented.The compound 1 that so obtains is equivalent to the modified siloxane compound by formula (1) expression, and finds to have 8500 weight-average molecular weight, and HLB is that 5 (theoretical values) and the solubleness in water are 1% or still less.Compound 1 has m=73 in the formula (1), n=6, R ₁=propylidene, a=8, b=0 and R ₂The structure of=Wasserstoffatoms.

Formula (A)

Formula (B)

CH ₂＝CHCH ₂-O-(C ₂H ₄O) ₆-H

Compound 2

Use glass and TM is housed and the container of whipping appts, synthetic compound 2 in the following manner.In this container, under the situation of platinum catalyst, synthesize compound 2 as main ingredient through addition reaction by the polysiloxane compound of following formula (C) expression with by the polyoxyethylene compound that following formula (D) is represented.The compound 2 that so obtains is equivalent to the modified siloxane compound by formula (1) expression, and finds to have 29400 weight-average molecular weight, and HLB is that 5 (theoretical values) and the solubleness in water are 1% or still less.Compound 2 has m=245 in the formula (1), n=28, R ₁=propylidene, a=6, b=0 and R ₂The structure of=Wasserstoffatoms.

Formula (C)

Formula (D)

CH ₂＝CHCH ₂-O-(C ₂H ₄O) ₆-H

Compound 3

Use glass and TM is housed and the container of whipping appts, synthetic compound 3 in the following manner.In this container, under the situation of platinum catalyst, synthesize compound 3 as main ingredient through addition reaction by the polysiloxane compound of following formula (E) expression with by the polyoxyethylene compound that following formula (B) is represented.The compound 3 that so obtains is the control compounds by the modified siloxane compound of formula (1) expression, and finds to have 7400 weight-average molecular weight, and HLB is that 5 (theoretical values) and the solubleness in water are 1% or still less.Compound 3 has m=65 in the formula (1), n=5, R ₁=propylidene, a=8, b=0 and R ₂The structure of=Wasserstoffatoms.

Formula (E)

Formula (B)

CH ₂＝CHCH ₂-O-(C ₂H ₄O) ₆-H

Compound 4

Use glass and TM is housed and the container of whipping appts, synthetic compound 4 in the following manner.In this container, under the situation of platinum catalyst, synthesize compound 4 as main ingredient through addition reaction by the polysiloxane compound of following formula (F) expression with by the polyoxyethylene compound that following formula (G) is represented.The compound 4 that so obtains is equivalent to the modified siloxane compound by formula (2) expression, and finds to have 47000 weight-average molecular weight, and HLB is that 9 (theoretical values) and the solubleness in water are 1% or still less.Compound 4 has p=349 in the formula (2), R ₃=Wasserstoffatoms, R ₄=propylidene, the structure of c=240 and d=0.

Formula (F)

Formula (G)

Compound 5

Use glass and TM is housed and the container of whipping appts, synthetic compound 5 in the following manner.In this container, under the situation of platinum catalyst, synthesize compound 5 as main ingredient through addition reaction by the polysiloxane compound of following formula (H) expression with by the polyoxyethylene compound that following formula (I) is represented.The compound 5 that so obtains is the control compounds by the modified siloxane compound of formula (2) expression, and finds to have 7700 weight-average molecular weight, and HLB is that 7 (theoretical values) and the solubleness in water are 1% or still less.Compound 5 has p=64 in the formula (2), R ₃=Wasserstoffatoms, R ₄=propylidene, the structure of c=30 and d=0.

Formula (H)

Formula (I)

Compound 6

Use glass and TM is housed and the container of whipping appts, synthetic compound 6 in the following manner.In this container, under the situation of platinum catalyst, synthesize compound 6 as main ingredient through addition reaction by the polysiloxane compound of following formula (J) expression with by the polyoxyethylene compound that following formula (K) is represented.The compound 6 that so obtains becomes the control compounds by the modified siloxane compound of formula (2) expression, and finds to have 50400 weight-average molecular weight, and HLB is that 7 (theoretical values) and the solubleness in water are 1% or still less.Compound 6 has p=439 in the formula (2), R ₃=Wasserstoffatoms, R ₄=propylidene, the structure of c=200 and d=0.

Formula (J)

Formula (K)

Compound 7

Use glass and TM is housed and the container of whipping appts, by following mode synthetic compound 7.In this container, under the situation of platinum catalyst, synthesize compound 7 as main ingredient through addition reaction by the polysiloxane compound of following formula (L) expression with by the polyoxyethylene compound that following formula (M) is represented.The compound 7 that so obtains is equivalent to the modified siloxane compound by formula (3) expression, and finds to have 49000 weight-average molecular weight, and HLB is that 6 (theoretical values) and the solubleness in water are 1% or still less.Compound 7 has q=7 in the formula (3), R ₅=propylidene, R ₆=propylidene, e=6, the structure of f=0 and r=52.

Formula (L)

Formula (M)

CH ₂＝CHCH ₂-O-(C ₂H ₄O) ₆-CH ₂CH＝CH ₂

Compound 8

Use glass and TM is housed and the container of whipping appts, synthetic compound 8 in the following manner.In this container, under the situation of platinum catalyst, synthesize compound 8 as main ingredient through addition reaction by the polysiloxane compound of following formula (N) expression with by the polyoxyethylene compound that following formula (O) is represented.The compound 8 that so obtains is equivalent to the modified siloxane compound by formula (3) expression, and finds to have 8800 weight-average molecular weight, and HLB is that 6 (theoretical values) and the solubleness in water are 1% or still less.Compound 8 has q=23 in the formula (3), R ₅=propylidene, R ₆=propylidene, e=18, the structure of f=0 and r=3.

Formula (N)

Formula (O)

Compound 9

Use glass and TM is housed and the container of whipping appts, synthetic compound 9 in the following manner.In this container, under the situation of platinum catalyst, synthesize compound 9 as main ingredient through addition reaction by the polysiloxane compound of following formula (P) expression with by the polyoxyethylene compound that following formula (O) is represented.The compound 9 that so obtains is the control compounds by the modified siloxane compound of formula (3) expression, and finds to have 49000 weight-average molecular weight, and HLB is that 7 (theoretical values) and the solubleness in water are 1% or still less.Compound 9 has q=18 in the formula (3), R ₅=propylidene, R ₆=propylidene, e=18, the structure of f=0 and r=21.

Formula (P)

Formula (O)

Compound 10

Use glass and TM is housed and the container of whipping appts, synthetic compound 10 in the following manner.In this container, under the situation of platinum catalyst, synthesize compound 10 as main ingredient through addition reaction by the polysiloxane compound of following formula (Q) expression with by the polyoxyethylene compound that following formula (O) is represented.The compound 10 that so obtains is the control compounds by the modified siloxane compound of formula (3) expression, and finds to have 55000 weight-average molecular weight, and HLB is that 6 (theoretical values) and the solubleness in water are 1% or still less.Compound 10 has q=24 in the formula (3), R ₅=propylidene, R ₆=propylidene, e=18, the structure of f=0 and r=20.

Formula (Q)

Formula (O)

Compound 11

Use glass and TM is housed and the container of whipping appts, synthetic compound 11 in the following manner.In this container, under the situation of platinum catalyst, synthesize compound 11 as main ingredient through addition reaction by the polysiloxane compound of following formula (R) expression with by the polyoxyethylene compound that following formula (S) is represented.The compound 11 that so obtains is equivalent to the modified siloxane compound by formula (3) expression, and finds to have 8800 weight-average molecular weight, and HLB is that 1 (theoretical value) and the solubleness in water are 1% or still less.Compound 11 has q=16 in the formula (3), R ₅=propylidene, R ₆=propylidene, e=2, the structure of f=0 and r=6.

Formula (R)

Formula (S)

Compound 12

Use glass and TM is housed and the container of whipping appts, synthetic compound 12 in the following manner.In this container, under the situation of platinum catalyst, synthesize compound 12 as main ingredient through addition reaction by the polysiloxane compound of following formula (T) expression with by the polyoxyethylene compound that following formula (U) is represented.The compound 12 that so obtains is the control compounds by the modified siloxane compound of formula (3) expression, and finds to have 7800 weight-average molecular weight, and HLB is that 6 (theoretical values) and the solubleness in water are 1% or still less.Compound 12 has q=8 in the formula (3), R ₅=propylidene, R ₆=propylidene, e=7, the structure of f=0 and r=7.

Formula (T)

Formula (U)

The weight-average molecular weight of every kind of compound measuring as above to be obtained by following mode.Put into the modified siloxane compound that to measure THF (THF) and leave standstill some hrs and make its dissolving preparation solution, in order to the sample that becomes 0.1 quality % concentration.Afterwards, with membranous filter (trade(brand)name: TITAN 2 Syringe strainers, PTFE, the 0.45 μ m of the solvent resistance of 0.45 μ m hole dimension; Can obtain from SUN-SRi) filtering solution, use this sample solution, under following condition, measure weight-average molecular weight.

Equipment: Alliance GPC 2695 (by the Waters manufactured).

Post: SHODEX KF-806M, continuous four posts (can obtain) from Showa Denko K. K.

Moving phase; THF (superfine).

Velocity of flow: 1.0ml/min.

Furnace temperature: 40.0 ℃.

Inject sample solution amount: 0.1ml.

Detector: RI (specific refractory power) detector.

Polystyrene standard sample: PS-1 and PS-2 (can obtain) from Polymer Laboratories company; Molecular weight: 7500000,2560000,841700,377400,320000,210500,148000,96000,59500,50400,28500,20650,10850,5460,2930,1300 and 580, totally 17 kinds.

The preparation of liquid compsn

Composition through using down tabulation to represent among 4-1～4-11 prepares liquid compsn, contains as above any aqueous solutions of polymers of preparation, as above synthetic modified siloxane compound or from the market available modified siloxane compound.Specifically; To show 4-1～4-11 ingredients listed mixes under the listed prescription in each table; And thoroughly stir, then using hole dimension is that strainer (trade(brand)name: HD CII can obtain from the Nihon Pall ltd) pressure filtration of 2.5 μ m is with the preparation liquid compsn.In table 4-1～4-11, " Mw " refers to weight-average molecular weight.

Table 4-1

Prescription (the unit: %) of liquid combination

Table 4-2

Prescription (the unit: %) of liquid compsn

Table 4-3

Prescription (the unit: %) of liquid compsn

Table 4-4

Prescription (the unit: %) of liquid compsn

Table 4-5

Prescription (the unit: %) of liquid compsn

Table 4-6

Prescription (the unit: %) of liquid compsn

Table 4-7

Prescription (the unit: %) of liquid compsn

Table 4-8

Prescription (the unit: %) of liquid compsn

Table 4-9

Prescription (the unit: %) of liquid compsn

Table 4-10

Prescription (the unit: %) of liquid compsn

Table 4-11

Prescription (the unit: %) of liquid compsn

The preparation of China ink

The listed composition of table 5 below mixing, and stirring up hill and dale, then using hole dimension is that strainer (trade(brand)name: HD CII can obtain from the Nihon Pall ltd) pressure filtration of 2.5 μ m is to prepare China ink 1～3.

Table 5

Ink formulations (unit: %)

* 1: acetylenediol ethylene oxide adduct (tensio-active agent can be from Kawaken Fine Chemicals Co., and Ltd obtains)

For liquid compsn that is as above obtained and China ink, with consonance CBVP type tensiometer, model A-1 (being made by Kyowa Interface Science ltd) measures the surface tension under its 25 ℃.As a result, the surface tension of finding all liquid compsns all is higher than all black surface tension.

Estimate

Stability in storage

Put into each liquid compsn that is as above obtained the container of TEFLON (trade(brand)name) system and under 60 ℃ temperature, left standstill 1 month.Afterwards, the state of liquid compsn is estimated stability in storage before the state of visual observation liquid compsn liquid compsn after it returns room temperature and the storage.Estimate stability in storage according to judgement criteria as follows.The result lists in table 6-1～6-4.

A: the transparency of liquid compsn does not change before and after storing.

B: the transparency of liquid compsn does not change before and after storing, and in liquid compsn, can see something of suspended substance but store the back.

C: after the storage, in the container of making by TEFLON (trade(brand)name), form settling.

Spray character

(state of hole face and jetting stability)

The print cartridge of ink-jet recording device (trade(brand)name: PIXUS 850i; Make by Canon Inc.) load with the various liquid compsns that as above obtain, and in the device of the repacking of the ink-jet recording device of packing into, the position is its cyan ink position.Afterwards, three of Office Planner (can obtain) from Canon Inc. loose page or leaf on, with default mode write down load be 50% be of a size of 18cm * 24cm images recorded.In this record, on a diffusing page or leaf, to clean the surface of record-header each time between the record with the flap of PIXUS 850i.Afterwards, be recorded in CF102 to the nozzle verification test figure of PIXUS 850i and go up (can obtain) from Canon Inc..The state on visual inspection record-header surface is to estimate the state of hole face when this writes down.Estimate the state of hole face according to judgement criteria as follows.The result lists among table 6-1～6-4.Visual inspection nozzle verification test pattern is to estimate jetting stability in addition.Judgement criteria is estimated jetting stability according to being described below.The result is shown among table 6-1～6-4.

(state of hole face)

A: almost do not have liquid compsn to exist around jet hole.

B: the drop that has the certain liq compsn around jet hole.

C: the liquid film that exists zonal liquid compsn around jet hole.

(jetting stability)

A: record can normally carry out, and in nozzle verification test pattern, has no breaking-up.

B: more visible breaking-ups in nozzle verification test pattern, but do not see any underproof injection.

C: visible obvious imperfect injection and breaking-up in nozzle verification test pattern, can not carry out normal record.

Scuff resistance

Each liquid compsn that as above obtains and Ge Mo as under the combination shown in 6-1～6-4 of tabulating use and form images in the following manner (benchmark evaluation image).The print cartridge of ink-jet recording device (trade(brand)name: BJ F900; Make by Canon Inc.) load with liquid compsn and China ink respectively.Be installed in ink-jet recording device to liquid compsn in the position of its yellow China ink, China ink is in its magenta ink position.Afterwards, use China ink,, form image with 100% record load at resolving power and the 8 road nonreturn recordings of 1200dpi * 1200dpi with the emitted dose of 4.5ng.After as above being used for China ink on the recording medium,,, also impose on by the zone of China ink imaging and on every side liquid compsn with the resolving power of 1200dpi * 1200dpi and 8 road nonreturn recordings and at 50% record load with the emitted dose of 4.5ng.The document image that is obtained was statically placed in room temperature following 1 day, and thereafter, image scratches under the so strong pressure of use with nail, so that can scratch recording medium at its non--posting field.The document image that visual observation so scratches is to estimate their scuff resistance.Judgement criteria according to as follows is estimated scuff resistance.The result is shown in table 6-1 in 6-4.

A: on imaging surface, do not stay the nail seal.

B: on imaging surface, leave the nail seal, but do not have colorant to be wiped off.

C: on imaging surface, leave the nail seal off, and colorant is wiped slightly.

D: colorant is obviously wiped off, but the surface of recording medium does not expose.

E: no problem when touching image gently, the surface exposure of recording medium when its non--posting field scratches scrub images under recording medium but the degree that colorant is wiped off makes when applying strong pressure.

Kinetic friction coefficient

Kinetic friction coefficient in the image-region of the document image of measuring as above to be obtained by following mode (benchmark evaluation image).Specifically, in the image-region of (benchmark review image), with respect to the kinetic friction coefficient of polymethylmethacrylate (PMMA) ball with surface property detector (trade(brand)name: HEIDONTRIBOGEAR type 14DR, make) measurement image by new eastern science strain.Setting puts on the normal load of PMMA ball at 50g; And its translational speed is at 2mm/sec; When it moves, act on the horizontal force of PMMA ball travel direction through the pressure transmitter measurement, the power of calculated level direction and the ratio of vertical forces are as kinetic friction coefficient.The value that obtains based on kinetic friction coefficient like this is shown among table 6-1～6-4.

Table 6-1

Evaluation result

The evaluation result of jetting stability all is " B " in embodiment 8 and 9.Yet for the breaking-up state of nozzle verification test pattern, embodiment 8 is less than embodiment 9.At that time, pyrogenic state on the observed and recorded head well heater under opticmicroscope found that the coking incidence was that embodiment 8 lacks than embodiment 9.

Table 6-2

Evaluation result

Jetting stability all is " B " in embodiment 29 and embodiment 30.Yet for the breaking-up state of nozzle check side-view, embodiment 29 is less than embodiment 30.Its reason is that the coking state on the record-header well heater is observed embodiment 29 and is better than embodiment 30 under opticmicroscope.

Table 6-3

Evaluation result

The evaluation result of jetting stability all is " B " in embodiment 54 and 55.Yet for the breaking-up state of nozzle verification test pattern, embodiment 54 lacks than embodiment 55.At that time, the coking state under opticmicroscope on the observed and recorded head well heater found that the coking incidence was that embodiment 54 lacks than embodiment 55.

Table 6-4

Evaluation result

Various liquid compsns and the various China ink that as above obtains used in combination shown in following table 7, by following mode form images (benchmark evaluation image).The print cartridge of ink-jet recording device (trade(brand)name: BJ F900; Make by Canon Inc.) difference filling liq compsn and China ink.Liquid compsn is installed on the Huang Mo position in the ink-jet recording device, and China ink is on the magenta ink position.Thereafter, using China ink, is 4.5ng in emitted dose, and under the resolving power of 1200dpi * 1200dpi, 8 road nonreturn recordings form the image of 100% record load down.After China ink as above is applied on the recording medium, be 4.5ng in emitted dose, under the resolving power of 1200dpi * 1200dpi, 8 road nonreturn recordings are applied to China ink with liquid compsn and form the zone of image and on every side with 25% record load down.On the document image that is obtained, by same way as with estimate its scuff resistance and kinetic friction coefficient according to as above identical judgement criteria.The result is shown in Table 7.

Table 7

Evaluation result

Various liquid compsns and the various China ink that as above obtains used in combination shown in following table 8, and by following mode form images (benchmark evaluation image).The print cartridge of ink-jet recording device (trade(brand)name: BJ F900; Make by Canon Inc.) load liquid compsn and China ink respectively.Liquid compsn is installed on the magenta ink position in the ink-jet recording device, and China ink is on its Huang Mo position.Thereafter, before China ink is applied to recording medium, be 4.5ng in emitted dose, in the resolving power of 1200dpi * 1200dpi, adopt 8 road nonreturn recordings with under 50% the recording power, be applied to China ink for use to liquid compsn and form the zone of image and on every side.After liquid compsn as above is used on the recording medium, use China ink, be 4.5ng in emitted dose, resolving power is 1200dpi * 1200dpi and 8 road nonreturn recordings, forms the image with 100% record load.For the document image that is obtained, estimate its scuff resistance and kinetic friction coefficient in the same manner with according to as above identical judgement criteria.The result lists in the table 8.

Table 8

Evaluation result

When under the optimum implementation of reference implementation example, the present invention being explained, be to be understood that the optimum implementation that the invention is not restricted to disclosed embodiment.The equivalent structures book is according to the wideest explanation so that comprise all such improvement projects and the 26S Proteasome Structure and Function of equivalence.

Claims (13)

1. liquid compsn, it comprises modified siloxane compound and polymkeric substance at least, wherein,

Said modified siloxane compound is to be selected from by the modified siloxane compound of following formula (1) expression, by the modified siloxane compound of following formula (2) expression and at least a by in the modified siloxane compound of following formula (3) expression,

Said polymkeric substance is to be selected from acid number with 90mgKOH/g～150mgKOH/g and is 1.0cal through the hydrogen bond item (δ h) that the monomer SP that constitutes polymkeric substance obtains polymkeric substance ^0.5/ cm ^1.5～3.7cal ^0.5/ cm ^1.5Polymer A and have greater than the acid number of 150mgKOH/g～200mgKOH/g and be 1.0cal through the hydrogen bond item (δ h) that the monomer SP that constitutes polymkeric substance obtains polymkeric substance ^0.5/ cm ^1.5～1.5cal ^0.5/ cm ^1.5Polymer B at least a,

Here, the modified siloxane compound by formula (1) expression has 8000～30000 weight-average molecular weight; In formula (1), R ₁Be alkylidene group with 1～20 carbon atom, R ₂Be Wasserstoffatoms or the alkyl with 1～20 carbon atom, m is 1～250, and n is 1～100, a be 1～100 and b be 0～100;

Here, have 8000～be lower than 50000 weight-average molecular weight by the modified siloxane compound of formula (2) expression; In formula (2), R ₃Be Wasserstoffatoms or alkyl independently of one another with 1～20 carbon atom, R ₄For having the alkylidene group of 1～20 carbon atom, p is 1～450 independently of one another, and c is 1～250, and d is 0～100; With

Here, have 8000～be lower than 50000 weight-average molecular weight and HLB by the modified siloxane compound of formula (3) expression and be 1～be lower than 7; In formula (3), R ₅Be Wasserstoffatoms or alkyl independently of one another with 1～20 carbon atom, R ₆For having the alkylidene group of 1～20 carbon atom, q is 1～100, and r is 1～100, e be 1～100 and f be 0～100.

2. according to the liquid compsn described in the claim 1, wherein, has 5～11 HLB by the modified siloxane compound of formula (1) expression.

3. according to the liquid compsn described in the claim 1, wherein, polymer A comprises at least a monomer that is selected from vinylbenzene, n-butyl acrylate and the benzyl methacrylate.

4. according to the liquid compsn described in the claim 1, wherein, polymer B comprises at least a monomer that is selected from vinylbenzene and the alpha-methyl styrene.

5. according to the liquid compsn described in the claim 1, wherein, based on the total mass of liquid compsn, the polymer content in liquid compsn (quality %) is 2.5 quality %～4.0 quality %.

6. according to the liquid compsn described in the claim 1, wherein, based on the total mass of liquid compsn, the content of modified siloxane compound (quality %) is 0.5 quality %～be lower than, 3.0 quality %.

7. image forming method, it comprises bestows pigment inks step on the recording medium and bestows the step on the recording medium to liquid compsn, and wherein, liquid compsn according to claim 1 uses as this liquid compsn.

8. according to the image forming method described in the claim 7, wherein, the step of bestowing liquid compsn on the recording medium is after the step of bestowing pigment inks on the recording medium, to accomplish.

9. according to the image forming method described in the claim 7, wherein, the China ink that will comprise the pigment and the polymkeric substance of the acid number with 90mgKOH/g～200mgKOH/g uses as pigment inks.

10. according to the image forming method described in the claim 7, wherein, bestow pigment inks and liquid compsn on the recording medium through ink jet method.

11. print cartridge, it comprises the wherein liquid compsn storage compartment of storing liquid compsn, and the liquid compsn that wherein is stored in the liquid compsn storage compartment is according to the described liquid compsn of claim 1.

12. record cell; It comprises the liquid compsn storage compartment of storing liquid compsn wherein and the record-header of atomizing of liquids compsn therefrom, and the liquid compsn that wherein is stored in the liquid compsn storage compartment is according to the described liquid compsn of claim 1.

13. ink-jet recording device; It comprises the liquid compsn storage compartment of storing liquid compsn wherein and the record-header of atomizing of liquids compsn therefrom, and the liquid compsn that wherein is stored in the liquid compsn storage compartment is according to the described liquid compsn of claim 1.

Images