CN102675970B - Ink composition, ink group and method for forming image - Google Patents

Abstract

The invention provides an ink composition, an ink group and a method for forming an image. The ink composition comprises self-dispersal polymer particles, colloidal silicon dioxide and colorant particles, wherein each self-dispersal polymer particle comprises a structural unit derived from hydrophilic monomers and a structural unit derived from hydrophobic monomers. The ink composition has excellent discharging property and effectively inhibits the deterioration of liquid repellency of an ink gun component.

Description

Composition for ink, ink group and method of ink jet image formation

Technical field

The present invention relates to composition for ink, ink group and method of ink jet image formation.

Background technology

In recent years, as the result of the requirement day by day increased of the raising to conservation of resources, environment protection, operational stability etc., ink transition is become aqueous product progress.As when oil base ink, mobility is comprised, stability in storage, film glossiness to the quality product that water-base ink requires, the transparency, tint permanence etc.But compared with oil base vehicle, with regard to pigment-dispersing etc., most of pigment has the suitability of significance difference to water-based vehicle, therefore, does not obtain gratifying quality product by conventional disperse method.In the past, examined the use of multiple additives such as water-based paint dispersion resin or tensio-active agent, but also do not obtained such water-base ink, it meets above-mentioned whole suitability and is equivalent to have the existing oil base ink of high product quality.

In order to address these problems, such as, disclosed a kind of aqueous ink composition, its contain as the tinting material coated by insoluble polymer of coloured material and polymer particle (see, such as, Japanese Patent Application Publication (JP-A) 2001-329199).In addition, disclosed composition for ink containing resin emulsion and inorganic oxide colloid (such as, see, Japanese Patent 3550637), and which depict and can form good image.

Summary of the invention

According to an aspect of the present invention, a kind of ink jet ink composition is provided, described ink jet ink composition comprises from monodisperse polymer particle, and each in monodisperse polymer particle described comprises the structural unit derived from hydrophilic monomer and the structural unit derived from hydrophobic monomer; Colloid silica; And colorant particle; Described ink jet ink composition has excellent discharge and inhibits the deterioration of the fluid-repellency of ink gun component.According to another aspect of the present invention, providing package containing the ink group of described ink jet ink composition, and uses the method for ink jet image formation of this ink jet ink composition.

Accompanying drawing explanation

Exemplary of the present invention is described in detail based on figure below, wherein:

Fig. 1 is the example cross section of an example of the internal structure of display ink gun; And

Fig. 2 is the schematic diagram of an example of the array of the relief outlet shown in nozzle piece.

Embodiment

Although by the scuff resistance using the aqueous ink composition described in JP-A2001-329199 to improve formed image, this aqueous ink composition talkative is gratifying in discharge property hardly.In addition, when composition for ink comprises polymer particle, during aqueous ink composition as described in Japanese Patent 3550637, the situation of existence is that the fluid-repellency of the liquid repellence film in ink gun component reduces.

The present invention considers said circumstances and carries out.One aspect of the present invention relates to provides a kind of composition for ink for ink-vapor recording, uses said composition, and discharge property is excellent and inhibits the decline of the fluid-repellency of ink gun component.In addition, another aspect of the present invention relates to ink group and the method for ink jet image formation that providing package contains described composition for ink.

Include but not limited to down list <1> to <14> according to the exemplary of this aspect of the invention.

<1> ink jet ink composition, described ink jet ink composition comprises from monodisperse polymer particle, colloid silica and colorant particle, each in monodisperse polymer particle described comprises the structural unit derived from hydrophilic monomer and the structural unit derived from hydrophobic monomer.

The ink jet ink composition of <2> according to <1> item is wherein more than 120 DEG C at the described second-order transition temperature from dispersed polymeres comprised in monodisperse polymer particle.

The ink jet ink composition of <3> according to <1> item or <2> item, wherein described comprise in monodisperse polymer particle from the I/O value of dispersed polymeres be 0.20 to 0.55.

The ink jet ink composition of <4> according to any one of <1> to <3> item, described ink jet ink composition in the pH value of the temperature of 25 DEG C in the scope of 7.5 to 10.

The ink jet ink composition of <5> according to any one of <1> to <4> item, the volume average particle size of wherein said colloid silica is below 25nm.

The ink jet ink composition of <6> according to any one of <1> to <5> item, wherein relative to the total mass of described ink jet ink composition, the content of described colloid silica is 0.005 quality % to 0.5 quality %.

The ink jet ink composition of <7> according to any one of <1> to <6> item, wherein by mass, the described colloid silica in described ink jet ink composition is 0.0001 to 0.1 relative to the described ratio of the content from monodisperse polymer particle (colloid silica/from monodisperse polymer particle).

The ink jet ink composition of <8> according to any one of <1> to <7> item, the wherein said structural unit derived from hydrophilic monomer comprises carboxyl.

<9>. the ink jet ink composition according to <8> item, wherein at the acid number from dispersed polymeres comprised in monodisperse polymer particle in the scope of 20mgKOH/g to 200mgKOH/g.

The ink jet ink composition of <10> according to any one of <1> to <9> item, the wherein said structural unit derived from hydrophobic monomer comprises cyclic aliphatic group.

The ink jet ink composition of <11> according to <10> item, wherein said hydrophobic monomer comprise (methyl) vinylformic acid bicyclic alkyl or have more than 3 ring (methyl) vinylformic acid multi-ring alkyl ester at least one.

<12> ink group, it comprises at least one in the ink jet ink composition according to any one of <1> to <11> item, with at least one treatment solution, described treatment solution is set to form aggregate when contacting with described ink jet ink composition.

<13> method of ink jet image formation, wherein the ink jet ink composition according to any one of <1> to <11> item is discharged to recording medium from being equipped with the ink gun of silicon nozzle piece, thus forms image.

Method of ink jet image formation described in <14> <13> item, described method also comprises: be applied to by treatment solution on described recording medium, described treatment solution can form aggregate when contacting with the ink jet ink composition according to <1> to <11> item.

< is used for the composition for ink > of ink-vapor recording

Composition for ink for ink-vapor recording of the present invention (below can referred to as " composition for ink ") is set to comprise at least one colorant particle, at least one comprise the structural unit derived from hydrophilic monomer and the structural unit derived from hydrophobic monomer from monodisperse polymer particle, with at least one colloid silica, and other component if desired.

By using the composition for ink with such formation, ink discharge property is excellent, and inhibits the reduction of the fluid-repellency of ink gun component.

Usually, fluid-repellency is given to keep ink jet performance to the component forming ink gun.This fluid-repellency can be given by such as using fluorochemical surface precision work agent process component surface.It is known that when long-time use ink gun, the fluid-repellency of ink gun component reduces gradually.

In addition, there is nozzle piece and be set to comprise silicon etc., accurately to form the situation of nozzle (relief outlet) meticulous especially.Equally, in the ink gun being equipped with the such nozzle piece formed by silicon etc., the situation that the reduction that there is the fluid-repellency of wherein nozzle piece has an impact to ink discharge property.

Even if when use is equipped with the ink gun of the such nozzle piece formed by silicon etc., the composition for ink for ink-vapor recording of the present invention also more effectively can suppress the reduction of the fluid-repellency of ink gun component.

[colloid silica]

Colloid silica is the colloid of the particulate comprised containing silicon inorganic oxide, and wherein the median size of particulate is below hundreds of nm.Colloid silica comprises silicon-dioxide (comprising its hydrate) as main ingredient, and can comprise aluminate as accessory constituent.Sodium aluminate and potassium aluminate can be comprised as the example of the involved aluminate of accessory constituent.

In addition, inorganic salt can be comprised as sodium hydroxide in colloid silica, potassium hydroxide, lithium hydroxide and ammonium hydroxide, or organic salt is as tetramethyl ammonium hydroxide.These inorganic salt and organic salt play a part such as deflocculant.

Dispersion medium for colloid silica is not particularly limited and can is water, organic solvent, or any one in the mixture of water and organic solvent.Organic solvent can be water-miscible organic solvent or water-insoluble organic solvents, but organic solvent is preferably water-miscible organic solvent.Its specific examples comprises methyl alcohol, ethanol, Virahol, and n-propyl alcohol.

The preparation method of colloid silica is not particularly limited, and colloid silica can be prepared by conventional method.Such as, colloid silica by aerosil (Aerosil) the synthesis preparation of wherein thermolysis silicon tetrachloride or can be prepared by water glass.Alternatively, colloid silica can according to comprise alkoxide hydrolysis liquid-phase synthesis process (see, such as, " Seni toKogyo ", the 60th volume, the 7th phase, the 376th page, 2004) etc. preparation.

The median size of the particle contained by colloid silica according to the present invention is not particularly limited.Such as, median size can be set to 1nm to 200nm.Median size is preferably 1nm to 100nm, is more preferably 3nm to 50nm, is also more preferably 3nm to 25nm, and is particularly preferably 5nm to 20nm.

When median size is below 200nm, can more effectively suppress by ink cause to forming the component of ink gun as substrate, protective membrane, the infringement (such as, degradation under fluid-repellency) of liquid repellence film etc.It is believed that, by making median size less, the total surface area of particle increases, thus more effectively inhibits the infringement to the component forming ink gun.In addition, also consider the discharge of composition for ink and suppress the abrasive effect caused by particle, the median size of preferred particle is below 200nm.In addition, when median size is more than 1nm, improve productivity, and the colloid silica showing less performance deviation (dispersion) can be obtained.

In the present invention, the median size of colloid silica is represented by volume average particle size.Volume average particle size can measure according to usual method such as light scattering method or the laser diffraction method for dispersed particle.

The shape of colloid silica is not particularly limited, as long as it does not disturb the jet performance of ink.Such as, shape can be spherical, long shape, the shape of needle-like, or the shape of similar pearl string.Especially, consider the discharge of ink, preferred colloid silica is spherical.

May be used for colloid silica of the present invention to be prepared by above-mentioned preparation method or can be commercial products.The specific examples of commercial products comprises LUDOX AM, LUDOX AS, LUDOX LS, LUDOX TM, and LUDOX HS (be all trade(brand)name, produced by E.I.Du Pontde Nemours & Co.); SNOWTEX S, SNOWTEX XS, SNOWTEX 20, SNOWTEX 30, SNOWTEX 40, SNOWTEX N, SNOWTEX C, and SNOWTEX O (be all trade(brand)name, produced by Nissan Chemical Industries, Ltd.); SYTON C-30 and SYTON ZOO (be all trade(brand)name, produced by Monsanto Co.); NALCOAG-1060 and NALCOAG-ID21 to 64 (be all trade(brand)name, produced by NalcoChem.Co.); METHANOL SOL, IPA SOL, MEK SOL, with TOLUENESOL (be all trade(brand)name, produced by Fuso Chemical Co., Ltd.), CATALOID-S, CATALOID-F120, CATALOID SI-350, CATALOID SI-500, CATALOIDSI-30, CATALOID S-20L, CATALOID S-20H, CATALOID S-30L, CATALOID S-30H, CATALOID SI-40, and OSCAL-1432 (Virahol colloidal sol) (be all trade(brand)name, produced by JGC Catalysts and Chemicals Ltd.); ADELITE (trade(brand)name is produced by Asahidenka Co., Ltd.); And the example of colloid silica as pearl string shape, SNOWTEX ST-UP, SNOWTEX PS-S, SNOWTEX PS-M, SNOWTEXST-OUP, SNOWTEX PS-SO, and SNOWTEX PS-MO (is all trade(brand)name, produced by Nissan Chemical Industries, Ltd.).These products easily obtain.

Usually be acid or alkaline pH by the pH regulator of above-mentioned commercially available colloid silica dispersion liquid.This is because the stable dispersion region of colloid silica is present in acidic side or alkaline side.When being joined in composition for ink by commercially available colloid silica dispersion liquid, the pH region of colloid silica stable dispersion and the pH of composition for ink should be considered.

The content of colloid silica in the composition for ink of exemplary of the present invention is not particularly limited.Such as, relative to the total mass of composition for ink, this content can be set to 0.0001 quality % to 10 quality %.Relative to the total mass of composition for ink, the content of colloid silica is preferably 0.001 quality % to 1 quality %, relative to the total mass of composition for ink, be more preferably 0.005 quality % to 0.5 quality %, and relative to the total mass of composition for ink, be particularly preferably 0.01 quality % to 0.1 quality %.When the content of colloid silica in composition for ink be equal to or less than above-mentioned in limited time, improve the discharge of composition for ink further, and can more effectively suppress by silicon dioxide granule the impact caused by the abrasive action of ink gun.In addition, when content is equal to or greater than above-mentioned in limited time lower, the reduction of the fluid-repellency of ink gun component can more effectively be suppressed.

In addition, consider suppression and the ink discharge property of the reduction of ink gun component fluid-repellency, preferred composition for ink of the present invention comprises with the amount of 0.001 quality % to 1 quality % the colloid silica that volume average particle size is 3nm to 25nm relative to the total mass of composition for ink.More preferably comprise with the amount of 0.005 quality % to 0.5 quality % the colloid silica that volume average particle size is 5nm to 20nm relative to the total mass of composition for ink.

[from monodisperse polymer particle]

Composition for ink for ink-vapor recording of the present invention comprises the particle of at least one from dispersed polymeres, describedly comprises the structural unit derived from hydrophilic monomer and the structural unit derived from hydrophobic monomer from dispersed polymeres.In addition, be set to comprise from monodisperse polymer particle such from dispersed polymeres (being called in some cases " the first polymkeric substance " below), describedly comprise at least one derived from the structural unit of hydrophilic monomer and at least one structural unit derived from hydrophobic monomer from dispersed polymeres.

When combining from monodisperse polymer particle, can form such composition for ink, using this composition for ink, discharge property is excellent, and the image formed has excellent scuff resistance.

Refer to when becoming dispersion state when there is no tensio-active agent by phase conversion emulsifying according to exemplary of the present invention from dispersed polymeres, the insoluble polymer of dispersion state in an aqueous medium can be in due to functional group's (especially, acidic-group or its salt) of polymkeric substance itself.

Here, term dispersion state comprises: wherein insoluble polymer is with liquid state dispersion emulsified state (emulsion) in an aqueous medium, and wherein insoluble polymer with solid state dispersion dispersion state (suspension) in an aqueous medium.

About exemplary according to the present invention from dispersed polymeres, consider from obtainable ink anchorage when being combined in composition for ink, preferably water insoluble polymer be can with solid state be in dispersion state from dispersed polymeres.

For the preparation of emulsification or dispersion state from dispersed polymeres namely from the method for the aqueous dispersion of dispersed polymeres can be phase conversion emulsifying.Phase inversion emulsification method can be a kind of such as so method: will be dissolved or dispersed in solvent (such as from dispersed polymeres, hydrophilic organic solvent etc.) in, when not adding tensio-active agent, solution or dispersion are introduced directly in water subsequently, mix under the condition stirring this system, neutralize by the salt formation group carried from dispersed polymeres (such as simultaneously, acidic-group), remove solvent, then obtain the aqueous dispersion being in emulsification or dispersion state.

The stable emulsion from dispersed polymeres in exemplary of the present invention or dispersion state refer to: even if when mixing is by being dissolved in the organic solvent of 70g (such as by the insoluble polymer of 30g, methyl ethyl ketone) the middle solution prepared, can in and the neutralizing agent of 100% salt formation group of insoluble polymer (if salt formation group is negatively charged ion, then neutralizing agent is sodium hydroxide, if or salt formation group is positively charged ion, then neutralizing agent is acetic acid), and 200g water, and stir (device: the whipping appts being equipped with agitating vane, rotating speed is 200rpm, last 30 minutes, 25 DEG C), when then removing organic solvent from liquid mixture, the state of emulsification or dispersion also keeps stablizing at least one week at 25 DEG C, therefore sedimentary generation can not be confirmed by Visual Observations Observations.

Can by confirming based on centrifugal precipitation accelerated test from the stability of the emulsification of dispersed polymeres or the state of dispersion.Can be evaluated by such as following process by the stability obtained based on centrifugal precipitation accelerated test: the solids concn aqueous dispersion of the polymer particle obtained by aforesaid method being adjusted to 25 quality %, subsequently by dispersion 12, centrifugal 1 hour of 000rpm, and the solids concn measuring the centrifugal supernatant liquor obtained afterwards.

During the ratio large (be worth close to 1) of the solids concn after centrifugal relative to the solids concn before centrifugal, this means the precipitation not have generation by the centrifugal polymer particle caused, that is, the aqueous dispersion of polymer particle is more stable.According to the present invention, the solids concn after centrifugal and centrifugal before the ratio of solids concn be preferably more than 0.8, more preferably more than 0.9, and be particularly preferably more than 0.95.

In addition, insoluble polymer refers to when polymkeric substance is at 105 DEG C of dry 2h, demonstrates the polymkeric substance of the meltage of below 10g when being then dissolved in the 100g water of 25 DEG C.This meltage is preferably below 5g, more preferably below 1g.Meltage is the meltage when polymkeric substance is neutralized to 100% according to the kind sodium hydroxide of the salt formation group of insoluble polymer or acetic acid.

Is such from dispersed polymeres according to exemplary of the present invention from dispersed polymeres: the content showing water miscible water soluble ingredient when becoming dispersion state is preferably below 10 quality %, more preferably below 8 quality %, also more preferably below 6 quality %.When water soluble ingredient is below 10 quality %, effectively suppress the fusion of the swelling of polymer particle or polymer particle, and more stable dispersion state can be kept.Can also suppress the increase of the viscosity of composition for ink, and jetting stability becomes better.

Here, water soluble ingredient refers to the compound be included in dispersed polymeres, and wherein this compound is dissolved in water when being in dispersion state from dispersed polymeres.Water soluble ingredient is with the water-soluble cpds that by product produces or is mixed in the production process from dispersed polymeres.

The second-order transition temperature of the first polymkeric substance (from dispersed polymeres) in illustrative embodiments of the invention is not particularly limited.But second-order transition temperature is preferably more than 120 DEG C, is more preferably 120 to 250 DEG C, is also more preferably 150 to 250 DEG C, and is even more preferably 160 to 200 DEG C.When second-order transition temperature is more than 120 DEG C, improve the resistance to blocking (especially, under high temperature and super-humid conditions) of formed image.In addition, when second-order transition temperature is below 250 DEG C, improve the scuff resistance of image.

The second-order transition temperature of the first polymkeric substance suitably can control according to common method.Such as, by suitably selecting the type of the polymerizable groups of the monomer of formation first polymkeric substance, the substituent type on monomer, form the ratio of monomer, the molecular weight etc. of polymer molecule, can be adjusted to the second-order transition temperature of the first polymkeric substance in required scope.

For the second-order transition temperature (Tg) of the first polymkeric substance of exemplary according to the present invention, use by actual measurement available measurement Tg.Particularly, the Tg of measurement refers to the value using differential scanning calorimeter (DSC) EXSTAR6220 (trade(brand)name) manufactured by SII Nanotechnology, Inc. to measure under usual measuring conditions.

But, if be difficult to due to the degraded etc. of polymkeric substance measure Tg, then use the calculating Tg calculated by following calculating formula.

The Tg calculated is calculated by following formula (1):

1/Tg＝∑(X _i/Tg _i) (1)

Here, assuming that in the polymkeric substance as calculating target, n kind monomer component (wherein i is 1 to n) copolymerization.X _ithe weight fraction (∑ Xi=1) of i-th kind of monomer, and Tg _ithe second-order transition temperature (absolute temperature) of the homopolymer of i-th kind of monomer, the condition summation that to be ∑ be from i=1 to i=n.In addition, for the second-order transition temperature (Tg of the homopolymer of each monomer _i) value, be used in the value provided in polymer handbook (Polymer Handbook) (third edition) (J.Brandrup, E.H.Immergut, (Wiley-Interscience, 1989)).

The I/O value of the first polymkeric substance in the present invention is not particularly limited.But described value is preferably 0.20 to 0.55, is more preferably 0.30 to 0.54, and is more preferably 0.40 to 0.50.

If the I/O value of the first polymkeric substance is more than 0.20, then can improve the stability of composition for ink.If I/O value is not more than 0.55, then resistance to blocking (especially, under high temperature and super-humid conditions) can increase.

I/O value, also referred to as inorganic value/organic value, is the value of the polarity representing various organic compound with organic conceptual manner, and is to the value in functional group's contribution approach of each functional group's setup parameter.

I/O value is described in more detail in " in organic conceptional diagram solution (Organic Conception Diagram) (KodaYoshio publishes (1984) by Sankyo Publishing Co., Ltd.) etc.The result that the representation of concept of I/O value is such: the character of compound is divided into the organic group representing covalent attachment performance and the inorganic group representing ionic bond performance, and using each organic compound as to have arbor and to evaluate without the point that the rectangular coordinates that arbor is formed is fastened.

Inorganic value be by evaluate by organic compound with various substituting group or key on the size of the impact of boiling point and the value this size being scaled the numeric data based on hydroxyl and obtaining.Particularly, when getting (take) distance between the boiling point curve and the boiling point curve of straight chain paraffins of straight chain alcohol near the compound at 5 carbon atoms, result is about 100 DEG C.Therefore, by the impact of a hydroxyl with the formal definition of numerical value for 100, and by by based on this value of 100 by various substituting group or various key the impact on boiling point be scaled numerical value and the value that obtains be used as by organic compound with substituent inorganic value.Such as, the inorganic value of-COOH base is 150, and the inorganic value of double bond is 2.Therefore, the inorganic value of certain class organic compound refer to by this compound with the summation of inorganic value of various substituting groups, key etc.

Organic value defines in the following manner: in units of the methylene radical in molecule, and will represent that the impact of carbon atom on boiling point of methylene radical is defined as benchmark.That is, when being added to by a carbon atom in the straight chain saturation alkane compound with about 5 to 10 carbon atoms, the mean value of the increasing amount of boiling point is 20 DEG C.Therefore, based on this value, the organic value of a carbon atom is defined as 20, and convert based on this value of 20 various substituting group or key are used as organic value to the value of the impact of boiling point.Such as, nitro (-NO ₂) organic value be 70.

I/O value close to 0 represents that organic compound is nonpolar (hydrophobicity, high Organic), and larger value represents that organic compound is polarity (wetting ability, high inorganic nature).

According to the present invention, the I/O value of the first polymkeric substance refers to the value measured by following method.Based on " organic conceptional diagram solution-basis and application (Organic ConceptionDiagram-Basis and Application)-(1984); the Organic (O value) described in the 13rd page and inorganic nature (I value), calculate the I/O value (=I value/O value) of each monomer of formation first polymkeric substance at Koda Yoshio.For each monomer forming polymkeric substance, calculate the product of (I/O value) and (in polymkeric substance % by mole), these products are sued for peace, and the value obtained by rounding up at the 3rd decimal is defined as the I/O value of the first polymkeric substance.

As the method for the inorganic value of each monomer of calculating, usually when adding, double bond is considered as the inorganic nature with 2; But, because double bond after polymerisation disappears, therefore use the value of the double bond part that do not add to calculate the I/O value of the first polymkeric substance used in the present invention as the inorganic value of monomer.

According to exemplary of the present invention, the polymkeric substance with required I/O value can be formed by suitably regulating the structure of the monomer of formation first polymkeric substance and content.

Consider from the stability of composition for ink, the resistance to blocking (particularly under a high temperature and high humidity condition) of image formed and scuff resistance, be preferably 120 to 250 DEG C according to the second-order transition temperature of the first polymkeric substance of exemplary of the present invention and its I/O value is 0.20 to 0.55.More preferably second-order transition temperature be 150 DEG C to 250 DEG C and I/O value is 0.30 to 0.54, and also more preferably second-order transition temperature be 160 DEG C to 200 DEG C and I/O value is 0.40 to 0.50.

At least one is comprised derived from the hydrophilic structure unit of hydrophilic monomer and at least one hydrophobic structure unit derived from hydrophobic monomer according to the first polymkeric substance of exemplary of the present invention.The main chain backbone of the first polymkeric substance is not particularly limited, but considers from the dispersion stabilization of polymer particle, and main chain backbone is preferably vinyl polymer, and is preferably (methyl) acrylic polymers.Here, (methyl) acrylic polymers refers to the polymkeric substance comprised derived from least one in the structural unit of methacrylic acid derivative and the structural unit of derived from propylene acid derivative.

(hydrophilic structure unit)

Hydrophilic structure unit is not particularly limited, as long as it is derived from the monomer containing hydrophilic radical, and it can be the unit derived from a kind of monomer (hydrophilic monomer) containing hydrophilic radical, or derived from the two or more unit containing the monomer of hydrophilic radical.Hydrophilic radical is not particularly limited, and it can be dissociation group or nonionic hydrophilic moieties.

In an exemplary embodiment of the present invention, from promoting that the stability of self-dispersing and the emulsification formed or dispersion state is considered, hydrophilic radical is preferably dissociation group, is more preferably negatively charged ion dissociation group.The example of dissociation group comprises carboxyl, phosphate, sulfonic group, and in them, considers, preferred carboxyl from anchorage when using composition for ink.

Consider from self-dispersing, the monomer containing hydrophilic radical in exemplary of the present invention is preferably the monomer containing dissociation group, preferably has the monomer containing dissociation group of dissociation group and ethylenic unsaturated link(age).

Example containing the monomer of dissociation group comprises unsaturated carboxylic acid monomer, unsaturated sulfonic acid monomer and unsaturated phosphorus acid monomer.

The specific examples of unsaturated carboxylic acid monomer comprises vinylformic acid, methacrylic acid, β-crotonic acid, methylene-succinic acid, toxilic acid, fumaric acid, citraconic acid and succsinic acid 2-(methacryloxy) methyl esters, etc.The specific examples of unsaturated sulfonic acid monomer comprises styrene sulfonic acid, 2-acrylamido-2-methyl propane sulfonic acid, (methyl) vinylformic acid 3-sulphopropyl and methylene-succinic acid two-(3-sulfapropyl) ester.The specific examples of unsaturated phosphorus acid monomer comprises vinyl phosphonate, phosphoric acid vinyl acetate, phosphoric acid two (methacryloxyethyl) ester, diphenyl phosphate-2-acryloyloxyethyl ester, diphenyl phosphate-2-methacryloyloxyethyl and di(2-ethylhexyl)phosphate butyl-2-acryloyloxyethyl ester.

Containing in the monomer of dissociation group, consider dispersion stabilization and jetting stability, preferred unsaturated carboxylic acid monomer, and at least one more preferably in vinylformic acid and methacrylic acid.

The example with the monomer of nonionic hydrophilic moieties comprises the ethylenically unsaturated monomers containing (gathering) vinyloxy group or polypropylene oxygen base, such as vinylformic acid 2-methoxy acrylate, vinylformic acid 2-(2-methoxy ethoxy) ethyl ester, methacrylic acid 2-(2-methoxy ethoxy) ethyl ester, ethoxy triglycol methacrylic ester, methoxy poly (ethylene glycol) (molecular weight: 200 to 1000) monomethacrylates and polyoxyethylene glycol (molecular weight: 200 to 1000) monomethacrylates; And there is the ethylenically unsaturated monomers of hydroxyl, such as (methyl) acrylate, (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 4-hydroxy butyl ester and (methyl) vinylformic acid hydroxy pentane ester, the own ester of (methyl) vinylformic acid hydroxyl.

Consider the stability of particle and the content of water soluble ingredient, the monomer with nonionic hydrophilic moieties is preferably the ethylenically unsaturated monomers at end with alkyl oxide, but not has the ethylenically unsaturated monomers of hydroxyl at end.

According to the hydrophilic structure unit of exemplary of the present invention preferably any one embodiment following: the embodiment only comprising the hydrophilic structure unit with negatively charged ion dissociation group, and not only the hydrophilic structure unit with negatively charged ion dissociation group but also the embodiment comprising the hydrophilic structure unit with nonionic hydrophilic moieties were comprised.

In addition, also preferably comprise the two or more embodiments with the hydrophilic structure unit of negatively charged ion dissociation group, or contain the embodiment of the two or more hydrophilic structure unit with negatively charged ion dissociation group combined and the hydrophilic structure unit with nonionic hydrophilic moieties.

Consider viscosity and stability in time, below 25 quality % are preferably at the content of the hydrophilic structure unit in dispersed polymeres, be more preferably 1 quality % to 25 quality %, be also more preferably 2 quality % to 23 quality %, and be particularly preferably 4 quality % to 20 quality %.

When polymkeric substance has two or more hydrophilic structure unit, the total content of preferred hydrophilic structural unit is in above-mentioned scope.

The hydrophilic structure unit with negatively charged ion dissociation group at the content in dispersed polymeres preferably making acid number fall in the scope of OK range described below.

Consider jetting stability and stability in time, the content with the structural unit of nonionic hydrophilic moieties is preferably 0 to 25 quality %, more preferably 0 to 20 quality %, and is particularly preferably 0 to 15 quality %.

When having negatively charged ion dissociation group from dispersed polymeres, consider from the anchorage when content of self-dispersing, water soluble ingredient and polymkeric substance composition composition for ink, acid number is preferably 20mgKOH/g to 200mgKOH/g, be more preferably 22mgKOH/g to 120mgKOH/g, and be also more preferably 25mgKOH/g to 100mgKOH/g.Acid number is particularly preferably 30mgKOH/g to 80mgKOH/g.When acid number is more than 20mgKOH/g, particle can more stably disperse, and when this acid number is below 200mgKOH/g, can reduce the content of water soluble ingredient.

(hydrophobic structure unit)

Hydrophobic structure unit according to exemplary of the present invention is not particularly limited, as long as it is derived from containing the monomer (hydrophobic monomer) of hydrophobic group, and can be can be maybe structural unit derived from the monomer containing two or more hydrophobic groups derived from the structural unit of the monomer containing a kind of hydrophobic group.Hydrophobic group is not particularly limited, and can be any one in chain linear aliphatic group, cyclic aliphatic group and aromatic group.

Consider from resistance to blocking, scuff resistance and dispersion stabilization, hydrophobic monomer according to exemplary of the present invention is preferably such hydrophobic monomer: its at least one is the monomer containing cyclic aliphatic base, be more preferably (methyl) acrylate (hereinafter, can be called " alicyclic (methyl) acrylate ") containing cyclic aliphatic base.

-alicyclic (methyl) acrylate-

Alicyclic (methyl) acrylate according to exemplary of the present invention is such compound, it comprises the structure position derived from (methyl) acrylic acid structure position and derive from alcohol, and has the structure containing at least one alicyclic alkyl not replacing or replace (cyclic aliphatic group) at the structure position of derive from alcohol.Alicyclic alkyl can be the structure position of derive from alcohol itself, or can be connected to the structure position of derive from alcohol via linking group.

" alicyclic (methyl) acrylate " refers to the methacrylic ester or acrylate with alicyclic alkyl.

Alicyclic alkyl is not particularly limited, as long as it comprises cyclic non-aromatic alkyl, and can be monocycle alkyl, dicyclo alkyl or there is the multi-ring alkyl of ring of more than three.

The example of alicyclic alkyl comprises cycloalkyl, such as cyclopentyl or cyclohexyl, cycloalkenyl group, dicyclohexyl, norcamphyl, isobornyl, bicyclopentane base, dicyclopentenyl, adamantyl, decahydronaphthalene naphthyl, perhydro fluorenyl, three ring [5.2.1.0 ^2,6] decyl, dicyclo [4.3.0] nonane etc.

Alicyclic alkyl can be substituted with a substituent further.Substituent example comprises alkyl, alkenyl, aryl, aralkyl, alkoxyl group, hydroxyl, primary amino, secondary amino group, uncle's amino, alkyl or aryl carbonyl, cyano group, etc.

Alicyclic alkyl can also form the ring condensed.

Consider from viscosity or resolvability, the alicyclic alkyl according to exemplary of the present invention preferably has 5 to 20 carbon atoms in clicyclic hydrocarbon base section.

The linking group connecting the structure position of alicyclic alkyl and derive from alcohol can be suitably alkylidene group, alkenylene, alkynylene, sub-aralkyl (arylalkylene group), alkylene oxide base (alkylenoxygroup), list-or oligomerisation of ethylene oxygen base, list-or oligomerisation of propene oxygen base, etc., it has 1 to 20 carbon atom.

Specific examples according to alicyclic (methyl) alkyl acrylate of exemplary of the present invention shows below, but the present invention is not limited to these examples.

The example of (methyl) vinylformic acid monocycle alkyl ester comprises (methyl) acrylate base ester that carbon atoms is the cycloalkyl of 3 to 10, such as (methyl) vinylformic acid ring propyl ester, (methyl) vinylformic acid ring butyl ester, (methyl) vinylformic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid ring heptyl ester, (methyl) vinylformic acid ring monooctyl ester, (methyl) vinylformic acid ring ester in the ninth of the ten Heavenly Stems and (methyl) vinylformic acid ring ester in the last of the ten Heavenly stems.

The example of (methyl) vinylformic acid bicyclic alkyl comprises (methyl) isobornyl acrylate, (methyl) vinylformic acid norborneol ester, etc.

The example of (methyl) vinylformic acid tricyclic alkyl ester comprises (methyl) vinylformic acid diamantane ester, (methyl) vinylformic acid two ring pentyl ester, (methyl) vinylformic acid dicyclopentenyl oxygen base ethyl ester, etc.

These can be used alone or use with its two or more mixture.

In these, consider from from the dispersion stabilization of monodisperse polymer particle, anchorage and resistance to blocking, preferably (methyl) vinylformic acid bicyclic alkyl and have more than 3 ring (methyl) vinylformic acid multi-ring alkyl ester at least one, and be more preferably selected from least one in (methyl) isobornyl acrylate, (methyl) vinylformic acid diamantane ester and (methyl) vinylformic acid two ring pentyl ester.

According to exemplary of the present invention, consider from the stable of the particle shape the stability from dispersion state, aqueous medium caused by the hydrophobic interaction between alicyclic alkyl and because the suitable hydropho of particle turns into the minimizing of caused water soluble ingredient amount, the content being included in the structural unit derived from alicyclic (methyl) alkyl acrylate in monodisperse polymer particle is preferably 20 quality % to 90 quality %, be more preferably 40 quality % to 90 quality %, and be particularly preferably 50 quality % to 80 quality %.

When the content of the structural unit derived from alicyclic (methyl) acrylate is more than 20 quality %, anchorage and adhesion can be improved.On the other hand, when the content of the structural unit derived from alicyclic (methyl) acrylate is below 90 quality %, the stability of polymer particle is improved.

Can be configured to also comprise other structural unit where necessary as hydrophobic structure unit except the structural unit comprised derived from alicyclic (methyl) acrylate from dispersed polymeres according to exemplary of the present invention.The monomer forming other structural unit is not particularly limited, if it be can with alicyclic (methyl) acrylate and the monomer of monomer copolymerization containing hydrophilic radical, and any known monomer can be used.

Form the monomer of other structural unit (hereinafter, also referred to as " other copolymerisable monomer ") specific examples comprise (methyl) alkyl acrylate, such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) isopropyl acrylate, (methyl) n-propyl, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) Ethyl acrylate, (methyl) EHA; Containing (methyl) acrylate of aromatic ring, such as (methyl) benzyl acrylate, (methyl) acrylate; Styrenic, such as vinylbenzene, alpha-methyl styrene, chloro-styrene; (methyl) propenoic acid dialkyl aminoalkyl ester, such as (methyl) acrylate; N-hydroxyalkyl (methyl) acrylamide, such as N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide, N-hydroxyl butyl (methyl) acrylamide; N-alkoxyalkyl (methyl) acrylic amide, such as N-methoxymethyl (methyl) acrylamide, N-ethoxyl methyl (methyl) acrylamide, N-(n-, different) butoxymethyl (methyl) acrylamide, N-methoxy ethyl (methyl) acrylamide, N-ethoxyethyl group (methyl) acrylamide, N-(n-, different) butoxyethyl group (methyl) acrylamide; Etc..

In them, consider from the snappiness of polymer backbone and the easiness of control second-order transition temperature (Tg), and consider from the dispersion stabilization from dispersed polymeres, the at least one that is preferably other structural unit contains (methyl) acrylate of the chain-like alkyl with 1 to 8 carbon atom, more preferably containing (methyl) acrylate of chain-like alkyl with 1 to 4 carbon atom, and (methyl) methyl acrylate or (methyl) ethyl propenoate is particularly preferably.Here, chain-like alkyl refers to the alkyl with straight or branched.

According to exemplary of the present invention, (methyl) acrylate containing aromatic group preferably can also be used.

When (methyl) acrylate containing aromatic group is included as other copolymerisable monomer, consider from the dispersion stabilization from monodisperse polymer particle, content derived from the structural unit of (methyl) acrylate containing aromatic group is preferably less than 40 % by weight, more preferably less than 30 % by weight, and be particularly preferably less than 20 % by weight.

In addition, when vinylbenzene-class monomer is used as other copolymerisable monomer, consider from the stability when dispersed polymeres is prepared into particle, content derived from the structural unit of vinylbenzene-class monomer is preferably below 20 quality %, more preferably below 10 quality %, more preferably below 5 quality %, and particularly preferably polymkeric substance does not comprise the structural unit derived from vinylbenzene-class monomer.

Here, vinylbenzene-class monomer refers to the vinylbenzene (alpha-methyl styrene, chloro-styrene, etc.) of vinylbenzene, replacement, or has the styrene macromer of polystyrene structural unit.

Other copolymerisable monomer according to exemplary of the present invention can be used alone or is used in combination with it.

When the first polymkeric substance comprises other structural unit, content is preferably 10 quality % to 80 quality %, is more preferably 15 quality % to 75 quality %, and is particularly preferably 20 quality % to 70 quality %.When combinationally using the monomer of the other structural unit of two or more formation, total content is preferably in above-mentioned scope.

Consider from dispersion stabilization, according to the first polymkeric substance of exemplary of the present invention preferably through the polymkeric substance being polymerized alicyclic (methyl) acrylate of at least three types, other copolymerisable monomer and obtain containing the monomer of hydrophilic radical, the polymkeric substance obtained more particularly by being polymerized alicyclic (methyl) acrylate of at least three types, (methyl) acrylate containing alkyl with the straight or branched of 1 to 8 carbon atom and the monomer containing hydrophilic radical.

According to exemplary of the present invention, consider from dispersion stabilization, preferably there is no that more preferably polymkeric substance does not comprise any described structural unit containing (methyl) acrylate of the straight or branched alkyl with more than 9 carbon atoms and the inclusion (content) with the substituent structural unit of high hydrophobicity derived from the macromonomer containing aromatic group etc.

Can be the random copolymers with each structural unit randomly introduced according to the first polymkeric substance of exemplary of the present invention, can be maybe the segmented copolymer with each structural unit introduced regularly.If the first polymkeric substance is segmented copolymer, then each structural unit can synthesize with certain introducing order, or identical formation component can use more than twice.But consider from versatility and productivity, preferably the first polymkeric substance is random copolymers.

With Weight-average molecular gauge, range preferably from 3,000 to 200,000 according to the molecular weight of the first polymkeric substance of exemplary of the present invention, be more preferably 10,000 to 200,000, and be more preferably 30,000 to 150,000.When weight-average molecular weight is 3, when more than 000, the amount of water soluble ingredient effectively can be suppressed.When weight-average molecular weight is 200, when less than 000, can improve from dispersion stabilization.

Here, weight-average molecular weight can pass through gel permeation chromatography (GPC) measurement.

Consider from the wetting ability and hydrophobicity that control polymkeric substance, according to the vinyl polymer that the first polymkeric substance of exemplary of the present invention is preferably such, it comprises the structure derived from alicyclic (methyl) acrylate that copolymerization ratio is 20 quality % to 90 quality %, and derived from containing dissociation group monomer structure and derived from containing have 1 to 8 carbon atom chain-like alkyl (methyl) acrylate structure at least one, and there is the acid number of 20 to 120, the total content of the hydrophilic structure unit of below 25 quality %, and 3, 000 to 200, the weight-average molecular weight of 000.

First polymkeric substance is more preferably such vinyl polymer, described vinyl polymer comprise copolymerization ratio be more than 20 quality % and be less than 90 quality % derived from dicyclo (methyl) acrylate or there is the structure of many rings (methyl) acrylate of ring of more than three, copolymerization ratio be more than 10 quality % and be less than 80 quality % derived from the structure of (methyl) acrylate comprising the chain-like alkyl with 1 to 4 carbon atom, and derived from the structure of carboxylic monomer, there is the acid number in the scope of 25 to 100, and there is the total content and 10 of the hydrophilic structure unit of below 25 quality %, 000 to 200, the weight-average molecular weight of 000.

And, first polymkeric substance is particularly preferably such vinyl polymer, described vinyl polymer comprise copolymerization ratio be more than 40 quality % and be less than 80 quality % derived from dicyclo (methyl) acrylate or there is the structure of many rings (methyl) acrylate of ring of more than three, copolymerization ratio be more than 20 quality % and at least one being less than 60 quality % derived from the structure of (methyl) methyl acrylate or (methyl) ethyl propenoate, and the structure of derived from propylene acid or methacrylic acid, there is the acid number in 30 to 80 scopes, and there is the total content and 30 of the hydrophilic structure unit of below 25 quality %, 000 to 150, the weight-average molecular weight of 000.

Below, the specific examples from dispersed polymeres will be enumerated with the form of exemplary compounds, but the present invention is not restricted to these.Value in bracket represents the mass ratio of copolymerization component.

Methyl methacrylate/isobornyl methacrylate/Sipacril 2739OF (20/72/8), second-order transition temperature: 180 DEG C, I/O value: 0.44

Methyl methacrylate/isobornyl methacrylate/Sipacril 2739OF (40/52/8), second-order transition temperature: 160 DEG C, I/O value: 0.50

Methyl methacrylate/isobornyl methacrylate/Sipacril 2739OF (50/44/6), second-order transition temperature: 140 DEG C, I/O value: 0.51

Methyl methacrylate/isobornyl methacrylate/Sipacril 2739OF (85/7/8), second-order transition temperature: 120 DEG C, I/O value: 0.67

Methyl methacrylate/benzyl methacrylate/Sipacril 2739OF (85/7/8), second-order transition temperature: 100 DEG C, I/O value: 0.67

Methyl methacrylate/methacrylic acid two ring pentyl ester/Sipacril 2739OF (20/72/8), second-order transition temperature: 160 DEG C, I/O value: 0.47

Methyl methacrylate/isobornyl methacrylate/methacrylic acid two ring pentyl ester/Sipacril 2739OF (20/62/10/8), second-order transition temperature: 170 DEG C, I/O value: 0.44

For the calculating of I/O value, use fol-lowing values as the I/O value of the monomer of formation polymkeric substance.

Methyl methacrylate: 0.60 isobornyl methacrylate: 0.29

Methacrylic acid two ring pentyl ester: 0.32 methacrylic acid: 0.47

For the preparation of being not particularly limited from the method for dispersed polymeres of exemplary according to the present invention, and polymkeric substance can be prepared by monomer mixture copolymerization according to known polymerization process.In these polymerization processs, consider from droplet jet performance when being formed as composition for ink, be more preferably polymerized in organic solvent, and particularly preferably solution polymerization process.

About the preparation method from dispersed polymeres of exemplary of the present invention, insoluble polymer as above can be prepared by the following method: make the mixture comprising monomer mixture and comprise organic solvent and radical polymerization initiator if desired carry out copolyreaction in inert gas atmosphere.

Method for the preparation of the aqueous dispersion from monodisperse polymer particle according to the present invention is not particularly limited, and can by the aqueous dispersion of known method acquisition from monodisperse polymer particle.The phase conversion emulsifying preferably including following procedures (1) and operation (2) from the method for dispersed polymeres is obtained with aqueous dispersion form.

Operation (1): obtain the operation of dispersion by stirring the mixture that comprises insoluble polymer, organic solvent, neutralizing agent and aqueous medium.

Operation (2): the operation removing organic solvent at least partially from dispersion.

The process that operation (1) is preferably such: first dissolved in organic solvent by insoluble polymer, adds neutralizing agent and aqueous medium lentamente wherein, and is mixed by mixture and stir to obtain dispersion.Thus, when adding neutralizing agent and aqueous medium in the solution to the insoluble polymer be dissolved in organic solvent, can when without the need to Strong shear power, obtain have the granularity of more high storage stability from monodisperse polymer particle.

The method stirred the mixture is not particularly limited, and can use any normally used mixing and whipping appts, or if desired, can use decollator, as ultrasonic dispersers or high-pressure homogenizer.

The preferred embodiment of organic solvent comprises alcoholic solvent, ketones solvent and ether solvent.

The example of alcoholic solvent comprises Virahol, propyl carbinol, the trimethyl carbinol, ethanol etc.The example of ketones solvent comprises acetone, methyl ethyl ketone, metacetone, methyl iso-butyl ketone (MIBK), etc.The example of ether solvent comprises dibutyl ether, diox etc.In these organic solvents, preferred ketones solvent such as methyl ethyl ketone, and alcoholic solvent such as Virahol.

Also preferably combination uses Virahol and methyl ethyl ketone.When combinationally using solvent, not assembling/precipitating or fusion between particle, and can obtain the particle size with high dispersion stability from monodisperse polymer particle.This is considered to because becoming gentle from oil phase to the change in polarity during phase inversion of aqueous phase.

Neutralizing agent is used to partially or completely and dissociation group, makes to form stable emulsification or the state of dispersion from dispersed polymeres in water.When exemplary of the present invention from dispersed polymeres, there is the negatively charged ion dissociation group as dissociation group, the example of the neutralizing agent used comprises basic cpd, such as organic amine compound, ammonia, alkali metal hydroxide.The example of organic amine compound comprises MMA, dimethylamine, Trimethylamine 99, mono aminoethane, diethylamine, triethylamine, single propylamine, dipropyl amine, monoethanolamine, diethanolamine, trolamine, N, N-dimethyl-ethanolamine, N, N-diethyl-thanomin, 2-diethylamino-2-methyl isophthalic acid-propyl alcohol, 2-amino-2-methyl-1-propanol, N methyldiethanol amine, N-ethyldiethanolamine, monoisopropanolamine, diisopropanolamine (DIPA) and tri-isopropanolamine, etc.The example of alkali metal hydroxide comprises lithium hydroxide, sodium hydroxide and potassium hydroxide.In them, considering from the stably dispersing of monodisperse polymer particle water from illustrative embodiments of the invention, preferred sodium hydroxide, potassium hydroxide, triethylamine and trolamine.

Based on the dissociation group of 100 % by mole, the usage quantity of these basic cpds is preferably 5 % by mole to 120 % by mole, is more preferably 20 % by mole to 100 % by mole, and is more preferably 30 % by mole to 80 % by mole.When content is more than 15 % by mole, show the effect of the dispersion stable of particle in water of sening as an envoy to, and when content is below 80 % by mole, obtain the effect reducing water soluble ingredient.

In operation (2), by adopting ordinary method such as distillation under reduced pressure, from the dispersion obtained operation (1), distill out organic solvent, cause phase in version to be aqueous systems thus, the aqueous dispersion from monodisperse polymer particle can be obtained.Organic solvent in the aqueous dispersion of gained substantially on be removed, and the amount of organic solvent is preferably below 0.2 quality %, is more preferably below 0.1 quality %.

According to the mean particle size from monodisperse polymer particle of exemplary of the present invention preferably in the scope of 1nm to 100nm, be more preferably 3nm to 80nm, be also more preferably 5nm to 60nm.Mean particle size is particularly preferably 5nm to 40nm.When median size is more than 1nm, improve productivity.In addition, when mean particle size is below 100nm, stability in storage is improved.

Be not particularly limited from the size-grade distribution of monodisperse polymer particle, and polymer particle can have wide size-grade distribution or monodispersed size-grade distribution.Water-insoluble particle can also be used with two or more form of mixtures.

Such as light scattering method can be used to measure from the mean particle size of monodisperse polymer particle and size-grade distribution.

In the composition for ink of exemplary of the present invention, preferably exist with the form being substantially free of tinting material from monodisperse polymer particle.

The self-dispersing from monodisperse polymer particle with excellence of exemplary of the present invention, and the dispersion stabilization of independent polymkeric substance is very high.But, such as, because the function as the so-called dispersion agent for stable dispersion pigment is not remarkable, if be present in composition for ink from dispersed polymeres with the form containing pigment according to exemplary of the present invention, then therefore may reduce the stability of composition for ink entirety widely.

Composition for ink for ink-vapor recording of the present invention can comprise independent one from monodisperse polymer particle, maybe can contain two or more such particle.

Consider from the glossiness of image, based on the composition for ink for ink-vapor recording, 1 quality % to 30 quality % is preferably from the content of monodisperse polymer particle in the composition for ink of exemplary of the present invention, be more preferably 2 quality % to 20 quality %, and be particularly preferably 2 quality % to 10 quality %.

In addition, in the composition for ink of exemplary of the present invention, colloid silica is preferably 0.0001 to 0.1 by mass relative to from the content ratio of monodisperse polymer particle (colloid silica/from monodisperse polymer particle), and is more preferably 0.001 to 0.05.

When colloid silica is relative to when being more than 0.0001 from the content ratio of monodisperse polymer particle, more effectively inhibit the reduction of the fluid-repellency of ink gun component.In addition, when content ratio is less than 0.1, discharge is further increased.

In the composition for ink of exemplary of the present invention, consider ink discharge property, stability of ink, and the suppression of the reduction of the fluid-repellency of ink gun component, preferred ink composition comprise acid number be 20 to 200 from monodisperse polymer particle, be the colloid silica of 3nm to 50nm with volume average particle size, and its content ratio (colloid silica/from monodisperse polymer particle) be 0.0001 to 0.1 in mass.More preferably composition for ink comprise acid number be 22 to 120 from monodisperse polymer particle, and volume average particle size is the colloid silica of 3nm to 25nm, and its content ratio is 0.001 to 0.05.

[colorant particle]

The composition for ink for ink-vapor recording of exemplary of the present invention comprises at least one colorant particle.

It is enough that colorant particle has by the function of painted formation image, and can use water-insoluble dye, colored fine particle, any one in water dispersible pigment etc.In the present invention, consider light fastness etc., water dispersible pigment is preferred.

The specific examples of water dispersible pigment comprises following pigment (1) to (4).

(1) encapsulated pigment, particularly, by pigment being joined in polymer particle the polymer emulsion of preparation, more specifically, the water dispersion of pigment by preparing to give wetting ability by the polymer layer in surface of pigments with insoluble polymer dispersant-coated pigment.

(2) self-dispersing pigments, particularly, on its surface, there is at least one hydrophilic radical and show the pigment of water dispersible when there is not dispersion agent, more specifically, mainly carbon blacks etc., it makes pigment be scattered in alone in water through surface oxidation treatment to give wetting ability.

(3) pigment of resin dispersion particularly, is the pigment of the water-soluble polymers dispersion of 50, less than 000 by use weight-average molecular weight.

(4) pigment of surfactant-dispersed, particularly, by using the pigment of surfactant-dispersed.

In the present invention, (1) encapsulated pigment and (2) self-dispersing pigments are described to preferred example, and (1) encapsulated pigment is described to particularly preferred example.

(encapsulated pigments)

The type of pigment is not particularly limited, and can use conventional known organic and mineral dye.

Particularly, can mention at middle pigment described such as JP-A2007-100071, especially, preferably use azo pigment, phthalocyanine pigment, anthraquinone pigment, quinacridone pigment and carbon black class pigment.

Insoluble polymer dispersion agent (below, also referred to as " dispersion agent ") be not particularly limited, as long as it is (following that it is insoluble polymer, can be called " the second polymkeric substance ") and can dispersed color, and conventional known insoluble polymer dispersion agent can be used.Insoluble polymer dispersion agent can be set to comprise hydrophobic structure unit and hydrophilic structure unit simultaneously.

Form the monomer of hydrophobic structure unit can be vinylbenzene-class monomer, (methyl) alkyl acrylate, containing aromatic group (methyl) acrylate, etc.

The monomer forming hydrophilic structure unit is not particularly limited, as long as it is the monomer containing hydrophilic radical.Hydrophilic radical can be non-ionic group, carboxyl, sulphonate-base, phosphonic acids alkali, etc.The definition of non-ionic group is with identical to the definition of the non-ionic group described from dispersed polymeres below.

Consider from dispersion stabilization, the hydrophilic structure unit according to exemplary of the present invention preferably at least comprises carboxyl, and also preferably comprises the form of non-ionic group and carboxyl simultaneously.

Vinylbenzene-(methyl) acrylic copolymer, vinylbenzene-(methyl) vinylformic acid-(methyl) acrylate copolymer, (methyl) acrylate-(methyl) acrylic copolymer, polyoxyethylene glycol (methyl) acrylate-(methyl) acrylic copolymer, styrene-maleic acid copolymer is comprised according to the specific examples of the insoluble polymer dispersion agent of exemplary of the present invention, etc.

Here, term " (methyl) vinylformic acid " refers to acrylic or methacrylic acid.

Consider from the dispersion stabilization of pigment, insoluble polymer dispersion agent according to exemplary of the present invention preferably wraps carboxylic vinyl polymer, more preferably such vinyl polymer, its at least have as hydrophobic structure unit derived from containing the structural unit of monomer of aromatic group and the carboxylic structural unit as hydrophilic structure unit.

Consider from the dispersion stabilization of pigment, the weight-average molecular weight of insoluble polymer dispersion agent is preferably 3,000 to 200, and 000, be more preferably 5,000 to 100,000, be also more preferably 5,000 to 80,000, and be particularly preferably 10,000 to 60,000.

Consider from the dispersiveness of pigment, ink tint permanence and dispersion stabilization, based on pigment, according to the content of the dispersion agent in the encapsulated pigments of exemplary of the present invention, 5 quality % to 200 quality % are preferably by dispersion agent, be more preferably 10 quality % to 100 quality %, and be particularly preferably 20 quality % to 80 quality %.

When the content of the dispersion agent in encapsulated pigments is in above-mentioned scope, pigment is by the dispersant-coated of appropriate amount, and therefore, the trend of existence easily obtains the encapsulated pigments with small grain size and excellent stability in time, and this is preferred.

Except comprising insoluble polymer dispersion agent, the encapsulated pigments according to exemplary of the present invention can also comprise another kind of dispersion agent.Such as, conventional known water-soluble low molecular weight dispersion agent can be used, or water-soluble polymers, etc.The content being different from the dispersion agent of insoluble polymer dispersion agent can use in the content range of above-mentioned dispersion agent.

If desired, other additive such as alkaline matter (neutralizing agent), tensio-active agent etc. can be added in encapsulated pigments.

For alkaline matter, neutralizing agent (organic bases, mineral alkali) can be used.In order in and the object of dispersion agent, preferably add alkaline matter, the pH regulator of the composition containing dispersion agent is 7 to 11 and more preferably adds alkaline matter, so that composition is adjusted to pH 8 to 10.

Based on the ionic group of the dispersion agent of 100 % by mole, the content of alkaline matter is preferably 50 to 150 % by mole, is more preferably 70 to 120 % by mole, and is particularly preferably 80 to 100 % by mole.

The specific examples of alkaline matter with to mention from monodisperse polymer particle those are identical.

(method for the preparation of the particle dispersion of coloured material)

Encapsulated pigments according to exemplary of the present invention can obtain with encapsulated pigments dispersion by using decollator to comprise the mixture dispersion of such as pigment, dispersion agent and solvent if desired (preferred organic solvent) etc.

Comprise pigment, dispersion agent, dissolving according to the particle dispersion (colorant particle dispersion) of the coloured material of exemplary of the present invention or disperse organic solvent and the alkaline matter of dispersion agent, and preferably by mixing containing the solution (mixing and hydration operation) as the water of main ingredient, then remove organic solvent (solvent removal operation) and prepare.

According to this method for the preparation of colorant particle dispersion, disperse encapsulated pigments subtly and therefore can prepare the colorant particle dispersion with excellent stability in storage.

The organic solvent used in the method for the preparation of colorant particle dispersion must dissolve or disperse the dispersion agent according to exemplary of the present invention, but in addition, preferred solvent also have to a certain degree with the affinity of water.Particularly, the solubleness in the water of 20 DEG C is preferably more than 10 quality % and below 50 quality %.

Colorant particle dispersion according to exemplary of the present invention can be prepared more particular by the preparation method comprising following shown operation (1) and operation (2), but described method is not limited to this.

Operation (1): dispersion treatment contains pigment, dispersion agent, dissolves or disperses the operation of the organic solvent of dispersion agent and the mixture of alkaline matter and water.

Operation (2): after dispersion treatment, removes the operation of organic solvent at least partially from mixture.

In operation (1), first, dispersion agent is dissolved or dispersed in organic solvent to obtain such mixture (mixed processes).Then, using containing pigment and alkaline matter and containing adding in mixture as the solution of the water of main ingredient and water and tensio-active agent etc. if desired, and by mixture mixing with disperse, to obtain the colorant particle dispersion of oil-in-water-type.

The addition (degree of neutralization) of alkaline matter is not particularly limited.Usually, preferably the liquid property of the encapsulated pigments dispersion of final gained is the liquid property close to neutrality, that is, such as pH (25 DEG C) is 4.5 to 10.PH can be determined by degree of neutralization according to dispersion agent.

The pigment used in the method for the preparation of colorant particle dispersion, dispersion agent are identical with those description in the part of colorant particle with other additive, and preferred embodiment is also identical.

The preferred embodiment of the organic solvent used in an exemplary embodiment of the present invention comprises alcoholic solvent, ketones solvent and ether solvent.In these, the example of alcoholic solvent comprises ethanol, Virahol, propyl carbinol, the trimethyl carbinol, isopropylcarbinol, diacetone alcohol, etc.The example of ketones solvent comprises acetone, methyl ethyl ketone, metacetone, methyl iso-butyl ketone (MIBK), etc.The example of ether solvent comprises dibutyl ether, tetrahydrofuran (THF), diox, etc.In these solvents, preferred Virahol, acetone and methyl ethyl ketone, and particularly preferably methyl ethyl ketone.

These organic solvents can be used alone, or combinationally use with several.

In the preparation of colorant particle dispersion, mediate dispersion treatment can use two roller mill, three-roll mill, ball mill, trommel grinding machine (throne mill), decollator (Disper), kneader, help kneader (cokneader), homogenizer, blender, single shaft or biaxial extruder etc., apply strong shearing force simultaneously and carry out.

In addition, to mediate and the details of dispersion has description in T.C.Patton " paint-flow and colo(u)rant dispersion (PaintFlow and Pigment Dispersion) " (1964, by John Wiley and Sons, Inc. publish) etc.

If desired, colorant particle dispersion can use vertical or horizontal sand mill, sell excellent pulverizer (pin mill), slit grinding machine (slit mill), ultrasonic dispersers etc., and utilize granularity for 0.01mm to 1mm and by glass, the bead that zirconium white etc. are formed carries out fine dispersion process.

In the method for the preparation of colorant particle dispersion of exemplary according to the present invention, removing of organic solvent is not particularly limited, and solvent can be removed by the such as distillation under reduced pressure of known method.

Encapsulated pigments in thus obtained colorant particle dispersion maintains good dispersion state, and gained colorant particle dispersion has excellent stability in time.

(self-dispersing pigments)

Self-dispersing pigments be its surface directly or be combined with many hydrophilic functional groups via alkyl, alkylether radicals, aryl etc. and/or its salt is (following, be called " dispersed give group ") pigment, and be the pigment dispersibled when not using dispersion agent in an aqueous medium.Herein, state " dispersibling in an aqueous medium when not using dispersion agent " and refer to the state dispersibled when not using the dispersion agent for dispersed color in an aqueous medium.

Do not need to comprise this dispersion agent as mentioned above in order to disperse common pigments to comprise further as the ink of tinting material owing to comprising self-dispersing pigments, therefore easily preparation has the ink of excellent jetting stability, the foaming caused by the defoaming wherein occurring hardly to be caused by dispersion agent reduces.

In the present invention, preferred example is described to by using the oxide treatment of hypohalous acid and/or hypohalite or having carried out surface-treated self-dispersing pigments by using the oxide treatment of ozone.Commercially available product can be used as self-dispersing pigments.The example of commercially available product comprises MICROJET CW-1 (trade(brand)name, produced by Orient Chemical Co.Ltd.), CAB-O-JET200 and CAB-O-JET 300 (be all trade(brand)name, produced by Cabot Oil & Gas Corp.).

According to exemplary of the present invention, the mean particle size of colorant particle is preferably 10nm to 200nm, is more preferably 10nm to 150nm, and is more preferably 10nm to 100nm.When mean particle size is below 200nm, colorrendering quality is gratifying, and when ink jet method, droplet jet performance is good.In addition, when mean particle size is more than 10nm, photostabilization is gratifying.

The size-grade distribution of colorant particle is not particularly limited, and can be any one in wide size-grade distribution and monodispersed size-grade distribution.The two or more colorant particle with monodispersed size-grade distribution can also be used as a mixture.

The mean particle size of colorant particle and size-grade distribution can such as use dynamic light scattering method to measure.

In the composition for ink of exemplary of the present invention, a kind of colorant particle can be used individually, or two or more colorant particle can be combinationally used.

Consider from the density of image, based on composition for ink, the content of the colorant particle in composition for ink is preferably 0.1 quality % to 25 quality %, be more preferably 1 quality % to 20 quality %, more preferably 1.5 quality % to 15 quality %, and be particularly preferably 1.5 quality % to 10 quality %.

In addition, from considerations such as the scuff resistances of image, colorant particle is preferably I/0.5 to 1/10 with from the content ratio of monodisperse polymer particle (colorant particle/from monodisperse polymer particle), and is more preferably 1/1 to 1/4.

[hydrophilic organic solvent]

The composition for ink for ink-vapor recording of exemplary of the present invention preferably comprises aqueous medium.Aqueous medium at least comprises water as solvent, but preferably comprises water and at least one hydrophilic organic solvent.Hydrophilic organic solvent is used to anti-drying dose, wetting agent or penetration enhancer.

Anti-drying dose or wetting agent are for preventing blocking caused when the ink jet orifice drying of the ink being used for ink-vapor recording at nozzle.Anti-drying dose or wetting agent are preferably the hydrophilic organic solvent of vapour pressure lower than water.

In addition, in order to the composition for ink being used in ink-vapor recording easily penetrates in paper, use hydrophilic organic solvent as penetration enhancer aptly.

It is 0.70 to the first hydrophilic organic solvent being less than 1.0 that the composition for ink for ink-vapor recording of exemplary of the present invention preferably comprises at least one I/O value.When the I/O value of the first hydrophilic organic solvent is less than 1.00, improves and the consistency from monodisperse polymer particle, more effectively improve the anchorage of formed image, and further increase the scuff resistance of image.When the I/O value of the first hydrophilic organic solvent is more than 0.70, improve the stability of composition for ink.

The I/O value of hydrophilic organic solvent is calculated in the mode identical with the calculating of the first polymkeric substance I/O value.

The composition for ink for ink-vapor recording of preferred exemplary of the present invention, except comprising the first hydrophilic organic solvent, also comprises the second hydrophilic organic solvent that at least one I/O value is 1.00 to 1.50.When the I/O value of the second hydrophilic organic solvent is more than 1.00, more effectively improve the stability of composition for ink.When the I/O value of the second hydrophilic organic solvent is less than 1.50, the deterioration of the anchorage of formed image can be suppressed.

I/O value is more than 0.70 and the specific examples being less than first hydrophilic organic solvent of 1.00 comprises glycol ethers.Preferred propylene glycol or glycol ether, and more preferably propylene glycol.Specific examples comprises tripropylene glycol (triprolene glycol) monomethyl ether (I/O value: 0.80), tripropylene glycol list ether (I/O value: 0.73), Tri(propylene glycol)butyl ether,mixture of isomers (I/O value: 0.61), dipropylene glycol (diprolene glycol) single ether (I/O value: 0.78), Dipropylene glycol mono-n-butyl Ether (I/O value: 0.70), and propylene glycol (prolene glycol) monobutyl ether (I/O value: 0.88).

In these, consider image anchorage and stability of ink, Tripropylene glycol monomethyl Ether (I/O value: be 0.80) preferred.

I/O value is that the specific examples of second hydrophilic organic solvent of 1.0 to 1.5 comprises propylene glycol monomethyl ether (I/O value: 1.50), dihydroxypropane single-ether (I/O value: 1.20), diethylene glycol monobutyl ether (I/O value: 1.40), triethylene glycol monobutyl ether (I/O value: 1.20), 2, 2-diethyl-1, ammediol (I/O value: 1.43), 2-methyl-2-propyl-1, ammediol (I/O value: 1.43), 2, 4-dimethyl-2, 4-pentanediol (I/O value: 1.43), 2, 5-dimethyl-2, 5-hexylene glycol (I/O value: 1.25), tripropylene glycol (I/O value: 1.33), SANNIXGP250 (trade(brand)name, I/O value: 1.30, by Sanyo Chemical Industries, Ltd. produce) etc.In them, consider image anchorage and stability of ink, SANNIX GP250 is preferred.

Consider image anchorage and stability of ink, the content for the first hydrophilic organic solvent in the composition for ink of ink-vapor recording of exemplary of the present invention is preferably 0.1 quality % to 20 quality %, be more preferably 1 quality % to 16 quality %, be also preferably 2 quality % to 12 quality %.

In addition, preferred ink composition using the amount of 1 to 16 quality % comprise its I/O value be selected from more than 0.70 and the hydrophilic organic solvent being less than the scope of 1.00 as the first hydrophilic organic solvent, and more preferably composition for ink comprises its I/O value with the amount of 2 quality % to 12 quality % and is selected from more than 0.70 and is less than the hydrophilic organic solvent of the scope of 0.90.

Consider image anchorage and stability of ink, the content for the second hydrophilic organic solvent in the composition for ink of ink-vapor recording in exemplary of the present invention is preferably 0.1 quality % to 20 quality %, be more preferably 1 quality % to 16 quality %, be also preferably 2 quality % to 12 quality %.

In addition, preferred ink composition comprises its I/O value using the amount of 1 to 16 quality % and is selected from the hydrophilic organic solvent of the scope of 1.00 to 1.50 as the second hydrophilic organic solvent, and more preferably composition for ink comprises with the amount of 2 quality % to 12 quality % the hydrophilic organic solvent that its I/O value is selected from the scope of 1.20 to 1.40.

In addition, consider image anchorage and stability of ink, the content ratio (the second hydrophilic organic solvent/the first hydrophilic organic solvent) for the second hydrophilic organic solvent in the composition for ink of ink-vapor recording and the first hydrophilic organic solvent is in an exemplary embodiment of the present invention preferably 1/10 to 10/1, be more preferably 1/4 to 4/1, and be also preferably 1/2 to 2/1.

Except the first hydrophilic organic solvent and the second hydrophilic organic solvent, the composition for ink for ink-vapor recording in exemplary of the present invention can also comprise other hydrophilic organic solvent.For other hydrophilic organic solvent, polyvalent alcohol can be used for playing a part anti-drying dose or wetting agent, and example comprises glycerine (I/O value: 5.00), ethylene glycol (I/O value: 2.00), glycol ether (I/O value: 5.00), triglycol (I/O value: 3.43), propylene glycol (I/O value: 2.50), dipropylene glycol (I/O value: 2.00), 1, 3-butyleneglycol (I/O value: 2.50), 2, 3-butyleneglycol (I/O value: 2.50), 1, 4-butyleneglycol (I/O value: 2.50), 3-methyl isophthalic acid, 3-butyleneglycol (I/O value: 2.00), 1, 5-pentanediol (I/O value: 2.00), Tetraglycol 99 (I/O value: 2.91), 1, 6-hexylene glycol (I/O value: 1.67), 2-methyl-2, 4-pentanediol (I/O value: 1.67), polyoxyethylene glycol (I/O value depends on the number of iterations of ethylidene chain), 1, 2, 4-trihydroxybutane (I/O value: 3.75), 1, 2, 6-hexanetriol (I/O value: 2.50) etc.These can use individually or can combinationally use with two or more.

In order to play a part the object of permeate agent, polyol compound is preferred, and the preferred embodiment of aliphatic diol comprises 2-Ethyl-2-Methyl-1, ammediol (I/O value: 1.67), 3,3-dimethyl-1,2-butyleneglycol (I/O value: 1.67), 5-hexylidene-1,2-glycol, 2-ethyl-1,3-hexylene glycol (I/O value: 2.00), and 2,2,4-trimethylammonium-1,3-pentanediol (I/O value: 1.88).

The content of other hydrophilic organic solvent can be such as, below 16 quality %, is preferably below 12 quality %, is more preferably below 8 quality %.

Can use individually for the hydrophilic organic solvent in the composition for ink of ink-vapor recording in exemplary of the present invention, or can use with two or more form of mixtures.Consider stability and jet performance, the content of hydrophilic organic solvent is preferably 1 quality % to 60 quality %, is more preferably 5 quality % to 40 quality %, and is particularly preferably 10 quality % to 30 quality %.

The addition of the water used in an exemplary embodiment of the present invention is not particularly limited, but consider and guarantee stability and spray reliability, for in the composition for ink of ink-vapor recording, described amount is preferably 10 quality % to 99 quality %, be more preferably 30 quality % to 80 quality %, and be also preferably 50 quality % to 70 quality %.

(other additive)

If desired, except comprising said components, the composition for ink for ink-vapor recording in exemplary of the present invention can also comprise other additive.

Known additive is comprised, such as fade inhibitor, emulsion stabilizer according to the example of other additive of exemplary of the present invention, penetration enhancer, UV light absorber, sanitas, mould resistant, pH adjusting agent, surface tension modifier, defoamer, viscosity modifier, dispersion agent, dispersion stabilizer, rust-preventive agent and sequestrant.These various additives directly can add after the composition for ink for the preparation of ink-vapor recording, or can add in the preparation process of the composition for ink for ink-vapor recording.Particularly, other additive etc. described in [0153] to [0162] section of JP-A 2007-100071 is included in.

Surface tension modifier can be nonionogenic tenside, cats product, anion surfactant, beet alkali surface activator, etc.

In order to satisfactorily composition for ink be got ready (spot) by ink jet method, the addition of surface tension modifier is preferably the addition of the surface tension adjustment of composition for ink to 20mN/m to 60mN/m, be more preferably the addition of surface tension adjustment to 20mN/m to 45mN/m, and be more preferably the addition of surface tension adjustment to 25mN/m to 40mN/m.

The surface tension of composition for ink can by use such as sheet method (plate method) 25 DEG C of measurements.

The specific examples of the tensio-active agent of hydro carbons preferably includes anion surfactant, such as soap, alkyl sulfuric ester salt, alkylbenzene sulfonate, sulfonated alkyl naphathalene, dialkyl sulfosuccinates, alkyl phosphate salt, naphthene sulfonic acid-formaline condensates and laureth sulfate; And nonionogenic tenside, as Voranol EP 2001, polyoxyethylene alkylallyl base ether, polyoxyethylene fatty acid ester, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkyl amine, glycerol fatty acid ester, oxygen ethylene oxy propylene-based block copolymer.Preferred use SURFYNOLS (trade(brand)name, the product of Air Products & Chemicals) and OLFINE E1010 (trade(brand)name, tensio-active agent, by Nissin Chemical Industry Co., Ltd. produce), they are acetylene class polyoxyethylene oxide tensio-active agents).In addition, the amphoterics of preferential oxidation amine, as N, N-dimethyl-N-alkyl amine oxide.

In addition, can be used in JP-A 59-157636 (37) discloses the material described in (Research Disclosure) 308119 (1989) as tensio-active agent to (38) page and research.

When use fluorohydrocarbon (alkyl fluoride RF class) tensio-active agent, silicone surfactant etc., such as describe in JP-A2003-322926,2004-325707 and 2004-309806 those time, can scuff resistance be improved.

Surface tension modifier can be used as defoamer, and the sequestrant etc. that can use fluorine cpd, silicone compounds, be represented by EDTA.

When ink be applied through ink jet method carry out time, consider droplet jet stability and aggregation velocity, the viscosity of the composition for ink in exemplary of the present invention is preferably in the scope of 1mPas to 30mPas, more preferably in the scope of 1mPas to 20mPas, also more preferably in the scope of 2mPas to 15mPas, and particularly preferably in the scope of 2mPas to 10mPas.

The viscosity of composition for ink can by such as Brookfield viscometer 20 DEG C of measurements.

Consider stability of ink and aggregation velocity, the pH of composition for ink is in an exemplary embodiment of the present invention preferably 7.5 to 10, and is more preferably 8 to 9.Note, the pH of composition for ink uses conventional pH meter (such as, MULTI-PARAMETER WATER QUALITYMETER MM-60R (trade(brand)name), is produced by DKK-Toa Corporation) to measure at 25 DEG C.

In addition, the pH of composition for ink suitably can be regulated by use acidic cpd or basic cpd.As acidic cpd or basic cpd, normally used compound can be used, and be not particularly limited.

< ink group >

Ink group in an exemplary embodiment of the present invention comprises at least one for the composition for ink of ink-vapor recording and at least one treatment solution, and described treatment solution is set to form aggregate when contacting the composition for ink for ink-vapor recording.

Ink group in an exemplary embodiment of the present invention uses in the image forming method using the composition for ink being used for ink-vapor recording, especially preferably as the ink group used in the image forming method described after a while.

Ink group in an exemplary embodiment of the present invention can use with the form of ink cartridge that is overall or that hold these inks independently, and preferred in view of the easiness of process.The ink cartridge being set to comprise ink group is known in correlative technology field, and can be prepared into ink cartridge by suitably using currently known methods.

-treatment solution-

Treatment solution is in an exemplary embodiment of the present invention the waterborne compositions forming aggregate when contacting the composition for ink for ink-vapor recording, and particularly, at least comprise gathering component, described gathering component can be gathered in the particle of the dispersed particle such as coloured material (pigment etc.) in composition for ink to form aggregate, and if desired, other component can be comprised.By using treatment solution together with composition for ink, ink-vapor recording can be accelerated, even and if when carrying out high-speed record, also obtaining and there is high-density and high-resolution image.

(gathering component)

Treatment solution comprises at least one and assembles component, and described gathering component, when contacting composition for ink, forms aggregate.By being mixed into by treatment solution in the composition for ink that sprayed by ink jet method, facilitate the gathering of the pigment of stable dispersion in composition for ink etc.

The example for the treatment of solution comprises the liquid composition that can be produced aggregate by the pH of change composition for ink.Therefore, consider the aggregation velocity of composition for ink, the pH (25 DEG C ± 1 DEG C) for the treatment of solution is preferably 1 to 6, is more preferably 1.2 to 5, and is more preferably 1.5 to 4.In this case, the pH (25 DEG C ± 1 DEG C) of the composition for ink used in injecting step is preferably 7.5 to 9.5 (being more preferably 8.0 to 9.0).

In an exemplary embodiment of the present invention, consider from the acceleration of image density, resolving power and ink-vapor recording, preferably, the pH (25 DEG C ± 1 DEG C) of composition for ink is more than 7.5, and the pH for the treatment of liq (25 DEG C ± 1 DEG C) is 3 to 5.

Assemble component can be used alone or in them two or more can by by their mixing use.

Treatment solution can use at least one acidic cpd to prepare as gathering component.As acidic cpd, the compound with phosphate, phosphonate group, phospho acid base, sulfate, sulfonic group, sulfino or carboxyl can be used, or its salt (such as, polyvalent metal salt).In them, consider that more preferably there is the compound of phosphate or carboxyl from the aggregation velocity of composition for ink, and preferably there is the compound of carboxyl.

The compound with carboxyl is preferably selected from polyacrylic acid, acetic acid, oxyacetic acid (glycoric acid), propanedioic acid, oxysuccinic acid, toxilic acid, xitix, succsinic acid, pentanedioic acid, fumaric acid, citric acid, tartrate, lactic acid, sulfonic acid, ortho-phosphoric acid, pyrrolidone formic acid, pyrone formic acid, minaline, furancarboxylic acid, pyridine carboxylic acid, coumaric acid (coumalic acid), thiophenic acid, nicotinic acid, or the derivative of these compounds, or their salt (such as, polyvalent metal salt etc.).One in these compounds can be used alone, or two or more in these compounds can use together.

Except above-mentioned acidic cpd, treatment solution in an exemplary embodiment of the present invention can also comprise aqueous solvent (such as, water).

Consider from congregation, based on the total mass for the treatment of solution, the content of acidic cpd in treatment solution is preferably 5 quality % to 95 quality %, and is more preferably 10 quality % to 80 quality %.

The preferred embodiment that can improve the treatment solution assembling at a high speed character comprises the treatment solution containing polyvalent metal salt or polyallyl amine.The example of polyvalent metal salt and polyallyl amine comprises the alkaline-earth metal of the 2nd race belonging to periodictable (such as, magnesium and calcium) salt, belong to the transition metal of periodictable the 3rd race (such as, lanthanum) salt, belong to periodictable the 13rd race metal (such as, aluminium) cationic salt, lanthanon (such as, neodymium) salt, PAH and polyallyl sulfonamide derivatives.As metal-salt, optimization acid's salt (as formate, acetate, benzoate), nitrate, muriate and thiocyanate-, more preferably the calcium salt of carboxylic acid or magnesium salts (as formate, acetate, benzoate), the calcium salt of nitric acid or the magnesium salts of nitric acid, the calcium salt of calcium chloride, magnesium chloride and thiocyanic acid or the magnesium salts of thiocyanic acid.

The content of metal-salt in treatment solution is preferably 1 quality % to 10 quality %, is more preferably 1.5 quality % to 7 quality %, and is more preferably 2 quality % to 6 quality %.

Consider from the aggregation velocity of composition for ink, the viscosity for the treatment of solution is preferably in the scope of 1mPas to 30mPas, more preferably in the scope of 1mPas to 20mPas, also more preferably in the scope of 2mPas to 15mPas, and particularly preferably in the scope of 2mPas to 10mPas.Described viscosity is measured under the condition of 20 DEG C by using VISCOMETER TV-22 (trade(brand)name is manufactured by TOKI SANGYOCO., LTD.).

Consider from the aggregation velocity of composition for ink, the surface tension for the treatment of solution is preferably 20mN/m to 60mN/m, is more preferably 20mN/m to 45mN/m, and is more preferably 25mN/m to 40mN/m.Surface tension is measured under the condition of 25 DEG C by using AUTOMATIC SURFACE TENSIOMETERCBVP-Z (trade(brand)name is produced by Kyowa Interface Science Co.Ltd.).

< method of ink jet image formation >

Method of ink jet image formation of the present invention is set to comprise by the above-mentioned composition for ink for ink-vapor recording is discharged step from being equipped with the ink gun of silicon nozzle piece to be ejected into recording medium is formed the ink of image, and comprises other step if desired.

In the present invention, preferred method of ink jet image formation also comprises treatment solution and applies step, that is, the treatment solution that can form aggregate in contact when the composition for ink of ink-vapor recording is applied to recording medium.

[ink discharge step]

Step discharged by ink is, by ink jet method, the above-mentioned composition for ink for ink-vapor recording is in an exemplary embodiment of the present invention applied to step recording medium from being equipped with the ink gun of silicon nozzle piece.In this step, composition for ink can optionally be applied on recording medium, and can form required visual picture.Each component in composition for ink of the present invention and the details of preferred embodiment described above.

The image recording of ink jet method is used to be ejected on required recording medium by liquid composition in particular by supplying energy and to carry out, described recording medium be common paper, resin-coated paper, such as at JP-A 8-169172,8-27693,2-276670,7-276789,9-323475,62-238783,10-153989,10-217473, the ink-vapor recording dedicated paper described in 10-235995,10-337947,10-217597 and 10-337947, film, electrofax common paper, fabric, glass, metal, pottery etc.As the ink jet recording method being applicable to exemplary of the present invention, the method described in JP-A2003-306623 (0093) to (0105) hurdle can be useful in.

Ink jet method is not particularly limited, and can have any known system, such as, utilize electrostatic attraction to spray the electric charge control system of ink; Utilize the vibration pressure of piezoelectric element and the system (pressure pulse system) of dripping as required; Electrical signal is transformed into acoustic beam, utilizes radiation pressure to spray the sound ink-jet system of ink their irradiation inks; With heating ink to form bubble and to utilize the hot ink-jet system (BUBBLEJET (registered trademark)) of pressure produced.It is the lower concentration ink droplet of small volume separately that the example of ink jet method comprises injection a large amount of, i.e. the system of so-called photo ink; Use multiple substantially the same tone and the ink with different concns improves the system of picture quality; And use the system of colorless transparent ink.

The ink gun used in ink jet method can be system or continuous system as required.Injection system specifically comprises such as, electromechanical converting system (such as, single chamber profile, dual cavity type, bender (bender) type, piston-type, sharing model type and shared wall-shaped, etc.), electric heating converting system (such as, hot inkjet type, BUBBLEJET (registered trademark) type, Deng), electrostatic attraction system (such as, electric field controls type, slit ejection-type, etc.), and Electronic control injection system (such as, spark ejection-type, etc.), and any one in injection system can be used.

For being had no particular limits by the ink nozzle etc. of ink jet method record, but can object be depended on and suitably choose.

The example of ink jet method comprises and uses short string type head and the ink jet method making described head carry out the reciprocation type system recorded while transversely the scanning of recording medium, and uses wherein recording element to be arranged in the ink jet method of the row system (linesystem) of the line head (line head) in the whole region of the side corresponding to recording medium.Be expert in system, can by allow recording medium with the direction at a right angle, direction of arrangement recording element on by scanning on the whole surface of recording medium document image, wherein do not need to use the transmission system being moved by short ink gun to carry out scanning, such as balladeur train (carriage).In addition, because the scan control of the complexity of the movement for balladeur train and recording medium is optional, and only there is recording medium to move, therefore compared to reciprocation type system, higher writing speed can be reached.Although ink jet recording method is in an exemplary embodiment of the present invention applicable to any one in them, but when ink jet recording method is applied to the row system of not carrying out false injection (dummy jetting), the effect improving the scuff resistance of accuracy of spray and image is normally significant.

In addition, discharge in step at the ink of exemplary according to the present invention, when using row system, not only use a kind of composition for ink, and use two or more composition for ink, by composition for ink (n-th kind of color (n >=1) of will first spray, such as, the second color) and the composition for ink that sprays subsequently ((n+1) plants color, such as, the third color) between injection (droplet jet) interval time be set as less than 1 second, suitably can carry out record.According to exemplary of the present invention, by the injection interval time being set as less than 1 second in method of being expert at, the image of the generation with excellent scuff resistance and repressed adhesion can be obtained, sprawling caused by the interference between simultaneously preventing by ink droplet or colour mixture under the speed obtained than routine high-speed record faster.In addition, the image with excellent color mediation drawing property (drawing properties) (fine rule in image or the reproducibility of fine portion) can be obtained.

Considering from obtaining high precision image, being preferably 0.5pL (skin liter) from the amount of the ink droplet of the ink of ink gun injection and, to 6pL, being more preferably 1pL to 5pL, and being more preferably 2pL to 4pL.

(being equipped with the ink gun of silicon nozzle piece)

The ink gun used in image forming method is in an exemplary embodiment of the present invention equipped with nozzle piece, and this nozzle piece is formed as making it comprise silicon at least partially.Fig. 1 is the schematic sectional view of an example of the internal structure of display ink gun.

As shown in Figure 1, ink gun 100 is equipped with the nozzle piece 11 and ink feed unit 20 with relief outlet (nozzle), and described ink feed unit 20 is arranged on the discharge direction opposition side of nozzle piece.In nozzle piece 11, be mounted with the relief outlet 12 of multiple discharge ink.

As shown in Fig. 2 typical case, nozzle piece 11 has 32 × 60 relief outlets (nozzle) of two-dimensional array form.Being formed by silicon at least partially of this nozzle piece.Nozzle piece has such structure, and wherein silicon is exposed to the inwall of nozzle opening and the sheet surface of ink discharge direction side.Although not display, the ink discharge direction side of nozzle piece 11 sheet surface at least partially on liquid repellence film is set.

Ink feed unit 20 is equipped with: multiple pressure chamber 21, and each pressure chamber is all communicated with each in multiple relief outlets 12 of nozzle piece 11 via nozzle communication channels 22; By the multiple ink feed passages 23 of each in ink feed to multiple pressure chamber 21; Ink feed is given the common liquid room 25 of multiple ink feed passage 23; And the Pressure generator 30 that each room in multiple pressure chamber 21 is out of shape.

Ink feed passage 23 is formed between nozzle piece 11 and Pressure generator 30, and is introduced in ink feed passage 23 by the ink being supplied to common liquid room 25.This ink feed passage 23 regulates the end of passage 24 to be connected with supply, and this supply regulates passage 24 to be connected with pressure chamber 21, therefore while the amount of the ink supplied by ink feed passage 23 is reduced to aequum, ink can be incorporated into pressure chamber 21.Multiple supply is set at ink feed passage 23 and regulates passage 24.Ink is supplied to the pressure chamber 21 be disposed adjacent with Pressure generator 30 via ink feed passage 23.

Therefore, multiple relief outlet can be given by a large amount of ink feeds.

Pressure generator 30 has such structure, wherein lamination vibrating plate 31, binder layer 32, lower electrode 33, piezoelectric body layer 34 and upper electrode 35 in the following order from side, pressure chamber 21.In addition, Pressure generator 30 is connected with the electric wire from outside supplies drive signals.When piezoelectric element is out of shape according to picture signal, ink is discharged from nozzle 12 via nozzle communication channels 22.

In addition, near relief outlet 12, circulation restrictor 41 is set, ink is constantly recovered in circuit 42.Thus ink thickening when preventing from not spraying near relief outlet.

-treatment solution applying step-

Treatment solution applies step by be applied to being set to be formed when contacting composition for ink the treatment solution (in some cases, referred to as treatment solution) of aggregate on recording medium and to make treatment solution contact composition for ink and carry out imaging.In this case, the dispersed particle of the polymer particle in composition for ink or coloured material (such as, pigment) is assembled, and by image set on the recording medium.In addition, the details of each component in treatment solution and preferred embodiment and upper described in.

The applying for the treatment of solution can be undertaken by using known method such as coating method, ink jet method and pickling process.Coating process can use the painting of coiling bar coater, extrusion die machine, Kohler coater, scraper plate coating machine, bar coater, knife coater, extrusion coating machine, reverse roll coating machine or coiling bar coater to be undertaken by known method.The details of ink jet method is described above.

Before or after treatment solution applying step can be arranged on the ink discharge step of use composition for ink.

In the present invention, preferably wherein ink is discharged step and be arranged in treatment solution applying step the embodiment after applying treatment solution.In other words, preferred following embodiment: wherein before composition for ink is discharged on recording medium, be applied for the treatment solution that the coloured material in composition for ink (preferred pigments) is assembled in advance, and discharge composition for ink and form image to contact the treatment solution that has been applied on recording medium.Thus, can ink-vapor recording be accelerated, even and if also obtain when carrying out high-speed record there is high-density and high-resolution image.

The applied amount for the treatment of solution is not particularly limited, as long as liquid can assemble composition for ink, but can be cause the applied amount of assembling component (cationic organic compound such as, more than carboxylic acid or divalence) to be 0.1g/m ²above amount.In them, the applied amount of assembling component is preferably caused to be 0.1g/m ²to 1.0g/m ²amount, and more preferably cause 0.2g/m ²to 0.8g/m ²amount.When the applied amount of assembling component is 0.1g/m ²time above, aggreation carries out satisfactorily, and equivalent is 1.0g/m ²time following, glossiness is not very high and is preferred.

According to exemplary of the present invention, preferably, ink is discharged step to be arranged on treatment solution and to apply after step, and time after treatment solution is applied on recording medium and the heat-drying step of the treatment solution on heating and dry recording medium is set between the time of discharging before composition for ink further.By to discharge before step heating and drying treatment liquid in advance at ink, ink coloring property such as prevents from sprawling and becomes good, and can record and have good colour density and the visual picture of tone.

Heating and the dry air-supply arrangement such as moisture eliminator that can pass through known heating unit such as well heater, utilization air-supply, or the device combining them carries out.The example of heating means comprises and applies hot method by well heater etc. from the recording medium contrary with the surface applying treatment solution surface, the surface of the recording medium applying treatment solution is blowed to the method for warm air or warm air, use the heating method of Infrared heaters, etc.Heating can also be undertaken by these methods of combination.

[adding thermal fixation step]

Preferred ink jet recording method in an exemplary embodiment of the present invention comprises and adds thermal fixation step after step discharged by ink, and this adds thermal fixation step for heating and set image by making the surface contact of ink image and the heating formed by applying composition for ink.By adding thermal fixation process, achieve image set on the recording medium, and the scuff resistance of image can be improved further.

Heating means have no particular limits, but can example aptly: non-contact drying method, such as uses the method for calorifier such as nickel chrom heater heating; The method of supply warm air or warm air; And use the method for the heating such as halogen lamp, infrared lamp.The method of heating and pressing is not particularly limited, but the method for being carried out heating and set by contact can be mentioned aptly, such as by method that the image formation surface of hot plate to recording medium presses, with the heating and the pressing belt that use the image capture surface side being equipped with a pair heating and pressing roller, a pair heating and pressing belt or be arranged on recording medium, and be arranged on the heating of maintaining roller of opposition side and press device and make image by the method for pair of rolls.

When using heating and pressing roller or heating and pressing belt, the transfer rate of recording medium preferably at 200mm/sec to 700mm/sec, more preferably 300mm/sec to 650mm/sec, and in the scope of preferred 400mm/sec to 600mm/sec.

-recording medium-

Ink jet recording method is in an exemplary embodiment of the present invention document image on the recording medium.

Recording medium is not particularly limited, and can use containing the general printing paper of Mierocrystalline cellulose as main ingredient, such as so-called high-quality paper, White Board and art paper.More slowly absorb and dry ink containing the general printing paper of Mierocrystalline cellulose as main ingredient, after drop is got ready, easily cause the movement of coloured material, and make picture quality in the image recording of the general ink jet method by using water-base ink easily deteriorated.But, according to ink-jet recording method in an exemplary embodiment of the present invention, inhibit the movement of tinting material and the high quality image with excellent color density and tone can be recorded.

As described recording medium, usual commercially available recording medium can be used, and example comprises high-quality paper as OK PRINCE HIGH QUALITY (trade(brand)name, by Oji Paper Co., Ltd. produce), SHIORAI (trade(brand)name, by Nippon Paper Industries Co., Ltd. produce), with NEW NP HIGH QUALITY (trade(brand)name, by Nippon Paper Industries Co., Ltd. produce), precise dipping paper is OK EVER LITE COAT (trade(brand)name such as, by Oji Paper Co., Ltd. produce) and AURORA S (trade(brand)name, Nippon Paper Industries Co., Ltd.), light White Board (A3) is OK COAT L (trade(brand)name such as, by Oji Paper Co., Ltd. produce) and AURORA L (trade(brand)name, by Nippon Paper Industries Co., Ltd. produce), White Board (A2, B2) such as OK TOP COAT+ (trade(brand)name, by Oji Paper Co., Ltd. produce) and AURORA COAT (trade(brand)name, by Nippon Paper Industries Co., Ltd. produce), and art paper (A1) such as OK KANEFUJI+ (trade(brand)name, by Oji Paper Co., Ltd. produce) and TOKUBISHI ART (trade(brand)name, by Nippon Paper Industries Co., Ltd. produce).In addition, the various developing out paper for ink-vapor recording can be used.

In them, from the effect of the movement suppressing coloured material large and obtain colour density and tone than before colour density and the better high quality image of tone consider, preferred absorption coerfficient Ka is 0.05mL/m ²ms ^1/2to 0.5mL/m ²ms ^1/2recording medium, more preferably absorption coerfficient Ka is 0.1mL/m ²ms ^1/2to 0.4mL/m ²ms ^1/2recording medium, and preferably absorption coerfficient Ka is 0.2mL/m ²ms ^1/2to 0.3mL/m ²ms ^1/2recording medium.

Absorption coerfficient Ka has as the identical meanings described in JAPAN TAPPI paper pulp testing method numbering 51:2000 (being published by JAPAN TAPPI), particularly, uptake factor Ka uses the difference of the transfer amount of autoscan absorptiometer KM500win (being produced by the Kumagai Riki Kogyo Co., Ltd.) transfer amount by the water of the duration of contact at 100ms and the water of the duration of contact at 900ms to calculate.

In the recording medium, the so-called White Board preferably used in common offset printing.White Board is the product obtained by the surface with coating material White Board such as high-quality paper or neutralized paper, and described high-quality paper or neutralized paper are mainly based on Mierocrystalline cellulose and without surface treatment.In the image of the employing aqueous inkjet recording of routine is formed, White Board easily causes product quality problem, the gloss of such as image or scuff resistance, but in ink-jet recording method in an exemplary embodiment of the present invention, inhibit lustre lacking uniformity, and obtain there is good gloss and the image of scuff resistance.Especially, the White Board of the coating that there is body paper and contain kaolin and/or Calcium hydrogen carbonate is preferably used.More specifically, more preferably art paper, White Board, light weight White Board or precise dipping paper.This is combined in by reference in the disclosure of the Japanese patent application 2009-217795 of submission on September 18th, 2009.

Embodiment

Below, describe the present invention particularly with reference to embodiment, but the invention is not restricted to these embodiments.Unless otherwise specified, otherwise " part " and " % " all in mass.

In addition, weight-average molecular weight is measured by gel permeation chromatography (GPC).HLC-8220GPC (trade(brand)name, produced by Tosoh Corp.) for GPC, and use TSK GEL SUPER HZM-H, TSK GEL SUPER HZ4000 and TSK GEL SUPER HZ2000 (trade(brand)name, all produced by Tosoh Corp.) as pillar, and three are connected in series.Elutriant is THF (tetrahydrofuran (THF)).For condition, sample concentration is 0.35 quality %, flow rate is 0.35ml/min, sample injection rate is 10 μ l, and measuring tempeature is 40 DEG C, and uses RI detector.Working curve is generated by 8 samples of following 2 standard model TSK standards: " polystyrene (polystyrene) ": " F-40 ", " F-20 ", " F-4 ", " F-1 ", " A-5000 ", " A-2500 ", " A-1000 " and " n-propylbenzene (n-propylbenzene) " (trade(brand)name), is produced by Tosoh Corp.

< is used for the preparation > of the composition for ink of ink-vapor recording

(synthesis of insoluble polymer dispersion agent P-1)

Be equipped with in the there-necked flask of agitator and cooling tube to 1000-ml, add the methyl ethyl ketone of 88g, and be heated to 72 DEG C under nitrogen atmosphere.Drip 2 of 0.85g wherein, 2 '-azo-bis-iso-dimethyl, 50g phenoxyethyl methacrylate, 13g methacrylic acid and 37g methyl methacrylate are dissolved in the solution in the methyl ethyl ketone of 50g, last 3 hours.After being added dropwise to complete, make mixture react 1 hour again, then add 2 of 0.42g wherein, 2 '-azo-bis-iso-dimethyl is dissolved in the solution in 2g methyl ethyl ketone.Temperature is increased to 78 DEG C, and mixture is heated 4 hours.The reaction soln of gained precipitates 2 times in excessive hexane, and by the resin drying of precipitation, to obtain the phenoxyethyl methacrylate/methyl methacrylate/Sipacril 2739OF (copolymerization ratio=50/37/13 by mass percentage) (pitch dispersant P-1) of 96.5g.

The composition of the pitch dispersant P-1 of gained passes through ¹h-NMR confirms, and is 49,400 by the weight-average molecular weight (Mw) that GPC determines.The acid number of multipolymer is determined by the method described in JIS standard (JISK0070:1992), and this value is 84.8mgKOH/g.

(preparation of colorant particle dispersion C)

Pigment Blue 15 by 10 parts: 3 (Phthalocyanine Blue A220, is produced by Dainichi SekaCo., Ltd.; Green pigment), the polymeric dispersant P-1 of 4 parts, the methyl ethyl ketone of 42 parts, the 1mol/L NaOH aqueous solution of 4.4 parts and the mixing of 87.2 parts of ion exchanged waters, and mixture to disperse 2 little of 6 hours by the zirconium white bead using diameter to be 0.1mm by ball mill.

Under reduced pressure and at 55 DEG C, from the dispersion of gained, remove methyl ethyl ketone, and remove part water further.Subsequently, use HIGH SPEED REFRIGERATED CENTRIFUGE7550 (trade(brand)name is produced by Kubota Corp.) and to use 50mL centrifuge tube to carry out 30min with 8000rpm centrifugal, thus except throw out except, recovery supernatant liquor.Subsequently, by absorption spectrum determination pigment concentration, be therefore that the dispersion of the pigment particles (encapsulated pigments) of the resin-coated of 10.2 quality % obtains colorant particle dispersion C with pigment concentration.

(preparation from monodisperse polymer particle)

The methyl ethyl ketone of 540.0g is incorporated into and is equipped with in 2 liters of there-necked flasks of agitator, thermometer, reflux condensing tube and nitrogen introducing tube, and under nitrogen atmosphere temperature is brought up to 75 DEG C.Temperature in maintenance reaction vessel is while 75 DEG C, dripping mixing solutions with constant rate of speed makes dropping complete in 2 hours, described mixing solutions is by " V-601 " (trade(brand)name of the isobornyl methacrylate (IBOMA) of the methyl methacrylate (MMA) of 216g, 280.8g, the methacrylic acid (MAA) of 43.2g, the methyl ethyl ketone of 108g and 2.16g, produced by Wako Pure ChemicalIndustries, Ltd.) formed.After being added dropwise to complete, add the solution formed by " V-601 " of 1.08g and the methyl ethyl ketone of 15.0g, and mixture is stirred 2 hours at 75 DEG C.The solution that further interpolation is formed by " V-601 " of 0.54g and the methyl ethyl ketone of 15.0g, and mixture is stirred 2 hours at 75 DEG C.Temperature is elevated to 85 DEG C, and continues stirring 2 hours.

The weight-average molecular weight (Mw) of gained multipolymer is 63,000 and acid number is 52.1mg KOH/g.

Then, weigh the polymeric solution of 588.2g, and add the NaOH aqueous solution of the Virahol of 165g and the 1mol/L of 120.8ml.Temperature in reaction vessel is elevated to 80 DEG C.Subsequently, drip 718g distilled water with the speed of 20ml/min, obtain the dispersion in water.Subsequently, the temperature in reaction vessel 80 DEG C keep 2 hours, keep 2 hours at 85 DEG C and keep while 2 hours at 90 DEG C, under atmospheric pressure distilling off solvent.Be reduced in the pressure of reaction vessel interior further and distill out Virahol, methyl ethyl ketone and distilled water, and obtaining the dispersion that solids concn is the example compound polymkeric substance (B-02) of 26.0%.

The second-order transition temperature of resulting polymers (B-02) is measured by method below and is 160 DEG C.

Count the polymers soln of the amount of 0.5g under reduced pressure in 50 DEG C of dryings 4 hours by after polymerization by solid part, obtain polymer solids part.Resulting polymers solid part is used to measure Tg with differential scanning calorimeter (DSC) EXSTAR 6220 (trade(brand)name) by being produced by SIINanotechnology, Inc..Measuring condition is: be sealed in aluminium dish by the sample of 5mg, and the value of the DDSC jag part in the take off data obtained when second time heats up in following temperature curve (profile) is under nitrogen atmosphere called Tg.

30 DEG C to-50 DEG C (cooling with 50 DEG C/min)

-50 DEG C to 230 DEG C (heating with 20 DEG C/min)

230 DEG C to-50 DEG C (cooling with 50 DEG C/min)

-50 DEG C to 230 DEG C (heating with 20 DEG C/min)

The dispersion from monodisperse polymer particle shown in following table 1 is prepared in the mode identical with from the dispersion of monodisperse polymer particle (B-02) when.In polymkeric substance composition in Table 1, MMA refers to methyl methacrylate, and IBOMA refers to isobornyl methacrylate, and DCPMA is methacrylic acid two ring pentyl ester, and BzMA refers to benzyl methacrylate, and MAA is methacrylic acid.Value refers to the ratio of components (by mass) of various monomer.

[table 1]

(preparation of non-self monodisperse polymer particle dispersion liquid D-1)

By the JONCRYL 537 of 200g, (trade(brand)name, is produced by BASF Japan Ltd.; Tg:49 DEG C, acid number: the 40) sodium oleate (tensio-active agent) of (pH:8.9), 9.0g and the ion exchanged water mixing of 191g, to prepare polymer particle dispersion liquid.Afterwards, being placed on by 200mL polymer particle dispersion liquid is of a size of in centrifugal polyethylene (poly) bottle of 250mL, and use HIGH SPEEDREFRIGERATED CENTRIFUGE 7750 (trade(brand)name, produced by KUBOTA Corporation) and HIGH CAPACITY ANGLE ROTOR AG-2506 (trade(brand)name) (centrifugal radius: 14.2cm) carry out the centrifugation of 1h with the rotating speed of 13,000rpm (centrifugal acceleration of 26830 × g).After centrifugation, by the supernatant liquor of 32 μm of nylon wires (trade(brand)name: N-NO380T, is produced by NBA) filtered polymeric particle dispersion, and filtrate is reclaimed.Thus, prepare the dispersion liquid D-1 of the non-self monodisperse polymer particle through centrifugal treating.

(preparation for the composition for ink of ink-vapor recording)

Use the pigment particles dispersion C of resin-coated, obtain as mentioned above from monodisperse polymer particle B-02 and colloid silica (" SNOWTEX C " (trade(brand)name), volume average particle size 15nm, by Nissan Chemical Industries, Ltd. produce), and mix various component to obtain following ink composition.Be filled in the disposable syringe be made of plastics, and by PVDF 5 μm of strainer (MILLEX-SV, trade(brand)name, diameter: 25mm, produced by Millipore Corp.) filter, to prepare cyan (composition for ink for ink-vapor recording) C-01.

-ink composition-

Green pigment (pigment Blue 15: 3): 4%

Polymeric dispersant P-1 (solid contents): 1.6%

The aqueous dispersion of polymer particle B-02 (solid contents): 5%

Colloid silica (solid contents): 1.5%

(trade(brand)name: SNOWTEX C is produced by Nissan Chemical Industries, Ltd., solid content 20%)

SANNIX GP250 ：10％

(trade(brand)name is produced by Sanyo Chemical Industries, Ltd., hydrophilic organic solvent, I/O value 1.30)

Tripropylene glycol monomethyl Ether (TPGmME): 6%

(being produced by Wako Pure Chemical Industries, Ltd., hydrophilic organic solvent, I/O value 0.80)

OLFINE E1010 ：1％

(trade(brand)name is produced by Nisshin Chemical Co., Ltd., tensio-active agent)

Ion exchanged water: for supplying the amount of altogether 100%

Respectively to prepare cyan C-02 to C-16 with above-mentioned substantially identical mode, difference is, use respectively cited by following table 2 from monodisperse polymer particle or non-self monodisperse polymer particle D-1 replace for the preparation of cyan C-01 from monodisperse polymer particle B-02, and the kind of the colloid silica for the preparation of cyan C-01 and amount to be replaced with those cited by following table 2 respectively.

-preparation for the treatment of solution (1)-

By various component mixing to obtain following composition, thus prepare treatment solution (1).The performance number of this treatment solution (1) is: the viscosity of such as 2.6mPas, the surface tension of 37.3mN/m and pH 1.6 (25 DEG C).

-composition for the treatment of solution (1)-

Propanedioic acid: 15.0%

(dibasic carboxylic acid is produced by Wako Pure Chemical Industries, Ltd.)

Diethylene glycol monomethyl ether: 20.0%

(being produced by Wako Pure Chemical Industries, Ltd)

N-oleoyl-N methyl taurine sodium: 1.0%

(tensio-active agent)

Ion exchanged water: 64.0%

< image is formed and evaluates >

Prepare the ink gun being equipped with silicon nozzle piece as shown in Figure 1, and recharge with the composition for ink obtained as mentioned above the storage tank being connected to ink gun.Note, use fluoroalkylsilane compounds, pre-set liquid repellence film on the surface of silicon nozzle piece." TOKUBISHIART DOUBLE-SIDED N " (trade(brand)name of recording medium will be used as, by Mitsubishi Paper Mills, Ltd. produce) paper be fixed on platform, described can the speed with 500mm/sec in predetermined rectilinear direction be moved.The temperature of platform remains on 30 DEG C.Coiling rod coating machine is used to be coated to the treatment solution obtained as mentioned above (1) with the thickness obtaining about 1.2 μm on recording medium, and after coating immediately 50 DEG C of dryings 2 seconds.

Afterwards, print out as follows and be of a size of 2cm ²50% solid (solid) image.Fix and settle ink gun, making the direction of the line of nozzle arrangement (the W direction in Fig. 2) relative to the direction (main scanning direction: X-direction in Fig. 2) vertical with the travel direction (sub scanning direction: the Y-direction in Fig. 2) of platform with the angular slope of 75.7 ° (90 ° of-α in Fig. 2).With constant speed along while sub scanning direction movable recording media, be 2.4pL at ink droplet quantity, discharge frequency and be 24kHz and under resolving power is the injection conditions of 1200dpi × 1200dpi, spray composition for ink by row system.After the printing, immediately by the recording medium of printing 60 DEG C of dryings 3 seconds, and to pass through between the set roller of 60 DEG C of heating at a pair further, thus with the gripping width of the clamp pressure of 0.25MPa and 4mm, carry out set process.By this way, the sample for evaluating is obtained.

(scuff resistance evaluation)

For the sample for evaluating obtained as mentioned above, after the printing, by " the TOKUBISHI ART DOUBLE-SIDED N " that do not print, (trade(brand)name, by Mitsubishi Paper Mills immediately, Ltd. produce) paper be placed on print surface, and with 150kg/m ²load rub back and forth 10 times.The degree that the scratch of Visual Observations Observations on the image printed and ink shift to the white background portions of non-printing record medium (untapped sample), and evaluate according to following judgement criteria.Evaluation result display in table 3.

It should be noted that evaluating C refers to practical problematic level.

-judgement criteria-

A: do not see scratch on the image printed, and do not confirm ink transfer at all.

B: the image printed is scratched slightly, but almost do not confirm significantly ink transfer.

C: the image printed obviously is scratched, and/or clearly confirm ink transfer.

(adhesion evaluation)

In the mode substantially similar with aforesaid way, the assess sample being entirely printed with 100% solid image is cut into the paper that 2 are of a size of 3.5cm × 4cm, and assess sample is arranged on be of a size of 10cm × 10cm (thickness 7mm) acrylic acid or the like plate on, make the surface of having printed facing with each other.The mode more than paper of the TOKUBISHI ARTDOUBLE-SIDED N (trade(brand)name is produced by Mitsubishi Paper Mills, Ltd.) do not printed 10 that are cut into same size covered is arranged in this assess sample further.The acrylic acid or the like plate that will be of a size of 10cm × 10cm (thickness 7mm) is mounted thereto further, and subassembly is left standstill 12 hours under 25 DEG C of envrionment conditionss with 50%RH.

After leaving standstill, by weight (the corresponding 700kg/m of 1kg ²weight) be arranged on acrylic acid or the like plate, and subassembly is left standstill 24 hours at the temperature as described in " the adhesion condition " in following table 3 and relative humidities further.

In addition, by the storage under ambient conditions 2 hour of subassembly at 25 DEG C and 50%RH, then by the TOKUBISHI ART (trade(brand)name, non-printing paper) that do not print overlayed in assess sample peel off.The easiness now peeled off by naked eye and the adhesion after stripping, and evaluate according to following standard.Result display in table 3.

-judgement criteria-

A: do not adhere on print surface.

D: adhere on print surface, and the attachment of paper can be confirmed by visual inspection.

(fluid-repellency evaluation)

-test of liquid repellence film immersion-

On the silicon chip being of a size of 2cm × 2cm, liquid repellence film (SAM film) is formed for the preparation of the sample evaluated by using fluoroalkylsilane compounds.Use prepared sample, according to the water contact angle that following method is measured on liquid repellence film.Evaluate composition for ink to the impact of the fluid-repellency of liquid repellence film.

Weigh the composition for ink of the 30ml of preparation as mentioned above, and place it in 50ml wide-necked bottle (trade(brand)name: AIBOI HIROKUCHI BIN 50mL, is produced by AS ONE Corporation).Then, above-mentioned sample is immersed in composition for ink, and leaves standstill 72 hours while 60 DEG C of heating.Afterwards, take out sample, with milli-Q water, and measure the water contact angle on the surface of liquid repellence film.

Water contact angle is measured, uses ultrapure water.Water contact angle uses contact angle instrument (trade(brand)name: DM-500, trade(brand)name, produced by Kyowa Interface Science Co., Ltd.) measured by usual method under 25 DEG C of environment with 50RH%, and evaluate according to following judgement criteria.

To it should be noted that in composition for ink the water contact angle before dipping is 106.5 degree, and to evaluate D be practical problematic level.

-judgement criteria-

More than AA:80 degree.

More than A:60 degree but lower than 80 degree.

More than B:40 degree but lower than 60 degree.

More than C:20 degree but lower than 40 degree.

D: lower than 20 degree.

(evaluation of discharge property)

To the ink gun of silicon nozzle piece be equipped with as shown in Figure 1 to fix, make the travel direction of platform on the direction perpendicular to nozzle arrangement direction.Note, use fluoroalkylsilane compounds, pre-set liquid repellence film at silicon nozzle piece.Subsequently, recharge with the composition for ink obtained as mentioned above the storage tank being connected to ink gun.Be fixed on platform by the paper of " KASSAI SHASHIN SHIAGE PRO " (trade(brand)name is produced by Fujifilm Corporation) that be used as recording medium, described can move up in the side perpendicular to nozzle arrangement direction.

Then, while with the speed transfer table of 248mm/min, ink droplet is sprayed with the resolving power of the injection frequency of the ink droplet quantity of 3.4pL, 10kHz and 75dpi × 1200dpi (nozzle arrangement direction × throughput direction), make each nozzle ejection 2000 ink droplets, 96 lines are printed in the direction being parallel to throughput direction, prepares printing sample thus.The printing sample of Visual Observations Observations gained, and confirm that ink is from all nozzle ejection.

After injection ink, by ink gun indwelling predetermined time under original state.Then another recording medium is fixed on platform, and again sprays ink under substantially the same conditions and prepare another printing sample.The printing sample of Visual Observations Observations gained.Determine after the indwelling scheduled time, the maximum time of repose that 96 nozzles all when injection 2000 ink droplets all can spray, used as the index for evaluating discharge property (discharge recovery).It is believed that not arrange out of order time of repose longer along with period, discharge property is better.Judgement criteria sets as follows.

It should be noted that evaluating D is practical problematic level.

-judgement criteria-

A: period, the out of order maximum time of repose of row did not occur is more than 45 minutes.

B: period the out of order maximum time of repose of row does not occur and is more than 30 minutes but is less than 45 minutes.

C: period the out of order maximum time of repose of row does not occur and is more than 20 minutes but is less than 30 minutes.

D: period the out of order maximum time of repose of row does not occur and is less than 20 minutes.

Be appreciated that from result above, when the composition for ink for ink-vapor recording in all uses exemplary of the present invention, define the image with excellent resistance to blocking and excellent scuff resistance.Also recognize, in these cases, discharge property is also excellent, and inhibits the reduction of the fluid-repellency of ink gun.

According to exemplary of the present invention, a kind of composition for ink for ink-vapor recording can be provided, comprise ink group and the method for ink jet image formation of described composition for ink, use this composition for ink, discharge property is excellent and inhibits the decline of the fluid-repellency of ink gun component.

The above-mentioned explanation of exemplary of the present invention has been provided in order to example and illustration purpose.It is not intended to be exhaustive, or limits the invention to disclosed precise forms.Select and describe embodiment, object is principle of the present invention and practical application thereof are described best, thus those skilled in the art can be made to understand each embodiment of the present invention, and the various amendments being applicable to specific end use are expections.

The all publications mentioned in this manual, patent application and technological standard are combined in this by reference, and its degree is as shown each such publication particularly and individually, and patent application or technological standard are to combine by reference.For those skilled in the art, it is evident that, many changes can be made in the details of the preferred embodiment of the invention described above.Intention is, scope of the present invention is by appended claim and equivalents thereof.

Claims (19)

1. an ink jet ink composition, described ink jet ink composition comprises:

From monodisperse polymer particle;

Colloid silica; And

Colorant particle,

Each in monodisperse polymer particle described comprises the structural unit derived from hydrophilic monomer and the structural unit derived from hydrophobic monomer,

Be wherein more than 120 DEG C at the described second-order transition temperature from dispersed polymeres comprised in monodisperse polymer particle,

Wherein by mass, the described colloid silica in described ink jet ink composition is 0.0001 to 0.1 relative to the described ratio of the content from monodisperse polymer particle (colloid silica/from monodisperse polymer particle).

2. ink jet ink composition according to claim 1, wherein described comprise in monodisperse polymer particle from the I/O value of dispersed polymeres be 0.20 to 0.55.

3. ink jet ink composition according to claim 1, described ink jet ink composition in the pH value of the temperature of 25 DEG C in the scope of 7.5 to 10.

4. ink jet ink composition according to claim 1, the volume average particle size of wherein said colloid silica is below 25nm.

5. ink jet ink composition according to claim 1, wherein relative to the total mass of described ink jet ink composition, the content of described colloid silica is 0.005 quality % to 0.5 quality %.

6. ink jet ink composition according to claim 1, the wherein said structural unit derived from hydrophilic monomer comprises carboxyl.

7. ink jet ink composition according to claim 6, wherein at the described acid number from dispersed polymeres comprised in monodisperse polymer particle in the scope of 20mgKOH/g to 200mgKOH/g.

8. ink jet ink composition according to claim 1, the wherein said structural unit derived from hydrophobic monomer comprises cyclic aliphatic group.

9. ink jet ink composition according to claim 8, wherein said hydrophobic monomer comprises (methyl) vinylformic acid bicyclic alkyl or has 3 with at least one in (methyl) vinylformic acid multi-ring alkyl ester of pressed on ring.

10. ink jet ink composition according to claim 1, wherein relative to the described total mass from monodisperse polymer particle, the content of the described structural unit derived from hydrophilic monomer is 1 quality % to 25 quality %.

11. ink jet ink compositions according to claim 1, the wherein said at least one comprised from monodisperse polymer particle in the group being selected from and being made up of the following: the structural unit derived from alicyclic (methyl) alkyl acrylate of 20 quality % to 90 quality %, derived from the structural unit of the monomer containing dissociation group with derived from containing the structural unit of (methyl) acrylate of chain-like alkyl with 1 to 8 carbon atom.

12. ink jet ink compositions according to claim 11, wherein relative to the described total mass from monodisperse polymer particle, described is 10 quality % to 25 quality % derived from the content of structural unit of (methyl) acrylate containing the chain-like alkyl with 1 to 8 carbon atom.

13. ink jet ink compositions according to claim 1, the wherein said weight-average molecular weight from dispersed polymeres is 3,000 to 200,000.

14. ink jet ink compositions according to claim 1, wherein described comprise in monodisperse polymer particle from the I/O value of dispersed polymeres be 0.20 to 0.55, and relative to the total mass of described ink jet ink composition, the content of described colloid silica is 0.005 quality % to 0.5 quality %.

15. ink jet ink compositions according to claim 1, wherein relative to the total mass of described ink jet ink composition, the content of described colloid silica is 0.005 quality % to 0.5 quality %, and at the described acid number from dispersed polymeres comprised in monodisperse polymer particle in the scope of 20mgKOH/g to 200mgKOH/g.

16. ink jet ink compositions according to claim 1, wherein at the described acid number from dispersed polymeres comprised in monodisperse polymer particle in the scope of 20mgKOH/g to 200mgKOH/g.

17. 1 kinds of ink groups, it comprises the ink jet ink composition according to any one of claim 1 to 16, and treatment solution, and described treatment solution is set to form aggregate when contacting with described ink jet ink composition.

18. 1 kinds of method of ink jet image formations, are wherein discharged to the ink jet ink composition according to any one of claim 1 to 16 recording medium from being equipped with the ink gun of silicon nozzle piece, thus form image.

19. method of ink jet image formations according to claim 18, described method also comprises: be applied to by treatment solution on described recording medium, described treatment solution can form aggregate when contacting with described ink jet ink composition.