CN107001830A

CN107001830A - Ink

Info

Publication number: CN107001830A
Application number: CN201580066494.6A
Authority: CN
Inventors: 克里斯托弗·奥里亚奇; 拉维·尚卡尔; 埃达·威尔逊; 迈克尔·芬尼根; 杰罗尔德·贝克尔; 基思·德兰尼; 安东尼·菲乌门尼罗; 菲利普·道部尔; 哈米德·施拉兹; 伊曼纽尔·迪莫塔科斯
Original assignee: Fujifilm Imaging Colorants Ltd
Current assignee: Fujifilm Imaging Colorants Ltd
Priority date: 2014-12-12
Filing date: 2015-12-10
Publication date: 2017-08-01
Also published as: TW201631062A; MX2017007120A; EP3230390A1; WO2016092309A1; KR20170098243A; JP2018505242A

Abstract

A kind of ink, including：(a) 0.5 to 5 part of self-dispersed pigment；(b) 2 to 8 parts of styrene acrylic latex adhesive and/or Styrene butadiene latexes adhesive；(c) 0.5 to 5 part of polyurethane latex adhesive；(d) 0 to 5 part of glycol, the glycol is selected from the group being made up of ethylene glycol, diethylene glycol (DEG), propane diols, dipropylene glycol or triethylene glycol；(e) 1 to 10 part of 2 pyrrolidones；(f) 1 to 15 part of glycerine；(g) 0.1 to 3 part of acetylenic surfactants；(h) 0.001 to 5 part of antimicrobial；(i) 0 to 10 part of viscosity modifier；The water of balance to 100 part (j).Present invention provides InkJet printing processes, jetted ink container, printed substrates and ink-jet printer.

Description

Ink

Technical field

Technique, jetted ink container, ink group and ink-jet printer the present invention relates to ink, for inkjet printing.

Background technology

Inkjet printing is a kind of non-back-strike print technology, and the wherein drop of ink is ejected into substrate by tiny nozzle On, without making nozzle and substrate contact.It basically there exist the inkjet printing of three types：

I) continuous inkjet printing, continuous inkjet printing is using pressurized ink source, and it produces the continuous of droplet of ink from nozzle Stream.Nominally the drop of ink is to be oriented from nozzle constant distance heat orientation or by electrostatic means.Deflect not successfully that A little drops are recycled to accumulator via groove.

II) drop on demand ink jet printing, wherein, ink is stored in print cartridge and the use of pressurized actuator (is typically heat or piezoelectricity ) sprayed from print-head nozzle.Drop on demand ink jet printing only produces the drop required for printing.

III) recycling inkjet printing, wherein ink is by continuously in printhead recycling and (such as in drop on demand ink jet printing In) drop required for printing is only retracted to nozzle.

The inkjet printing of these types proposes the challenge of uniqueness.Therefore, it is necessary to carry out oil in continuous inkjet printing Black active solvent monitoring and regulation, during the flight to resist the drop for not producing from nozzle ejection but print image (i.e. Nozzle sprays and groove reclaim between time) and exhaust process solvent evaporation, wherein being removed by exhaust process excessive Air when untapped drop (reclaim be drawn into accumulator).

In print on demand, ink may be maintained in print cartridge for a long time, and it can go bad and form sediment, sediment The thin nozzle that can block in use in printhead.This problem is especially serious when with pigment ink, wherein the pigment suspended Particle can be settled.

Recycling inkjet printing avoids these problems.Because ink is constantly circulated, it alleviates the machine of pigment sedimentation Meeting, and because ink only moves to nozzle to form image when needed, so solvent evaporation is minimized.

Recycling ink-jet printer has found particular utility in industrial quarters.Industrial inkjet printer needs high speed operation.Most It is desirable that for the printhead of industrial inkjet printer by multiple nozzles with high-density arrangement to realize with acceptable The high production rate one way printing of print resolution.

Ink formulations for the inkjet printing of form of ownership are extremely harsh.Especially being difficult to preparation can be high at these The ink of fast one way printhead work.In order that these printers are capable of the work of high speed, the ink used must show low Blowing potential and excellent droplet formation.

The content of the invention

Therefore, the invention provides the pigment ink of preparation with：

(i) nozzle blockage in recycling head will not be caused；

(ii) rapid draing is allowed by more more volatile than standard ink jet inks ink.This is essential in industrial processes , because it can realize high production speed and low energy consumption (i.e. low temperature is printed)；

(iii) by mixing well-chosen latex and obtaining the Gao Pin of high-durability by optimizing ink carrier design The image of matter, the flexographic plate that matches in excellence or beauty printing；

(iv) sufficiently stable and stalwartness, so that it can be used in continuous industrial environment；

(v) foaming is not caused；

(vi) panel in printhead will not be caused to soak.

The wettability of liquid is function of the surface tension of liquid relative to the surface energy of the surface of solids.Therefore, if should The molecule of liquid and the molecule of the surface of solids have the attraction (adhesion than cohesive force stronger) more stronger than between fluid molecule, then Occurs the wetting on surface.If however, stronger than occurring between fluid molecule and the molecule of the surface of solids between fluid molecule Ground attracts (cohesive force specific strength is stronger), then liquid formation liquid pearl and nonwetting surface.It can be placed on by measurement The contact angle of the drop of liquid on surface determines the degree of wetting of the liquid in particular surface.When contact angle is less than 90 degree When, it is believed that liquid soaks the surface.Contact angle is smaller, and wetness degree is bigger.

It is to have to challenge to design the volatility ink (required in (ii) and (iii)) containing low film formation temperature latex , its do not foam and nonwetting printhead panel.

Therefore, according to the first aspect of the invention there is provided a kind of ink, it is included：

(a) 0.5 to 5 part of self-dispersed pigment；

(b) 2 to 8 parts of styrene acrylic latex adhesive and/or Styrene butadiene latexes adhesive；

(c) 0.5 to 5 part of polyurethane latex adhesive；

(d) 0 to 5 part of the glycol selected from the group being made up of ethylene glycol, diethylene glycol (DEG), propane diols, dipropylene glycol and triethylene glycol；

(e) 1 to 10 part of 2-Pyrrolidone；

(f) 1 to 15 part of glycerine；

(g) 0.1 to 3 part of acetylenic surfactants；

(h) 0.001 to 5 part of antimicrobial；

(i) 0 to 10 parts of viscosity modifier；With

(j) water of balance to 100 parts.

All parts and percentages (unless otherwise indicated) herein are by weight.

Embodiment

" self-dispersed pigment " is pigment preparation, when being added in liquid medium, and it is free to, promptly and forever Ground disperses.If pigment carries charged group (directly or via associated polymeric dispersant) in its surface, it It is preferred that with counter ion counterionsl gegenions.

Self-dispersed pigment is preferred from the third edition of color index (1971) and subsequent revised edition and supplement in mark The pigment of any classification described under entitled " pigment " chapters and sections.

The example of suitable organic pigment is：Azo (including bisazo, condensation azo), thioindigo, indanthrone, different cloudy pellet Ketone, anthanthrone, anthraquinone, isodibenzanthrone, Molecular orbit, quinacridone and phthalocyamine series, particularly copper phthalocyanine and its Core halide derivative, and acid, alkalescence and mordant dye.Although carbon black is often regarded as being inorganic, but carbon black is in its point Scattered aspect of performance behaves much like organic pigment and is also suitable.It is preferred that organic pigment be phthalocyanine (particularly copper phthalocyanine Pigment), AZOpigments, indanthrone, anthanthrone, quinacridone and charcoal blacks.

The pigment is preferably yellow, cyan, magenta or black pigment.Pigment can be single chemical substance or contain The mixture (e.g., including mixtures of two or more different pigment) of two or more chemical substances.In other words, two kinds Or a variety of different pigment solids can be used in the technique of the present invention.

It is highly preferred that self-dispersed pigment is selected from by carbon black, pigment blue 15:3rd, pigment blue 60, pigment yellow 74, pigment yellow 155, In the group of paratonere 254 and pigment red 122 composition.

Pigment in self-dispersed pigment can be scattered by any mode known in the art.This can be related in pigment Suitable dispersant or their mixture are coated on surface.Dispersant can be anionic, cationic or non-ionic , and random, block or comb polymer can be included.Including but not limited to poly- (methyl) acrylic acid of suitable dispersant Ester, polyurethane, polyester and polyethers.

Other preferred self-dispersed pigments can be prepared by the surface of chemical modification pigment.This is special for carbon black It is preferred that, wherein can be with the surface of oxygenated pigment so that carbon black is water dispersible.Suitable oxidant includes air, peroxidating Hydrogen, hypochlorite, nitric acid, nitrogen dioxide, ozone and persulfate.

Therefore, in a preferred embodiment of the invention, self-dispersed pigment is the oxidized carbon black in surface.

Organic pigment can also have charged group, using the pigment for the particular category/type reagent or use Charged group is incorporated into their surface by more generally reacting for such as sulfonation.

Alternatively, the charged group or polymer that self-dispersed pigment can have chemical covalent to be attached to its surface disperse Agent.

Thus, for example, carbon black can be with diazonium reactant salt.This allows the surface that specific charged group is incorporated into carbon black On.Phenyl spacer group is generally used together with being bound to powered/dispersing group of phenyl.The example of this charged group is sulphur Hydrochlorate base, carboxyl, phosphate and diphosphonate.It can also use diazonium chemistry thing that a series of polymeric dispersants are introduced into charcoal Black surface.

Some organic pigments can also have the charged group being incorporated into via diazonium chemistry thing on their surface and gather Compound dispersant.Any class well known by persons skilled in the art that the dispersant for being attached to the surface of self-dispersed pigment can be Type.Dispersant can be general or be designed as being used together with specific pigment.

In a preferred embodiment of the invention, self-dispersed pigment is that have covalently to be attached to face by diazonium compound The charged group on the surface of material or the pigment of polymeric dispersant.

A kind of preferred form of dispersant is diblock copolymer A-B or triblock copolymer A-B-A, and wherein B block has There is the compatibility to pigment, and block A is responsible for colloid-stabilised.Organic pigment can synthesize the specific face including such dispersant Material, rather than in the step of dispersant is attached to pigment in post synthesis.

Preferably, in component (a), self-dispersed pigment includes dispersant of the crosslinking around pigment.

In a particularly preferred embodiment, in component (a), self-dispersed pigment is included by cross-linking agents in face Expect the carboxyl-functional dispersant around core, crosslinking agent, which has, is selected from oxetanyl, carbodiimide, hydrazide group, oxazole Quinoline base, '-aziridino, NCO, N- methylols, aziridine base, isocyanurate group and epoxide group (particularly two Individual or multiple epoxide groups) at least two groups.

Before being crosslinked with crosslinking agent, dispersant preferably has at least 125mg KOH/g acid number.

Dispersant preferably has one or more oligomeric dispersing groups.

In order to provide water dispersible, the granules of pigments of polymer encapsulating preferably has carboxylic group (in not being dispersant All carboxyls be all crosslinked with formed polymer encapsulating granules of pigments).

The granules of pigments of polymer encapsulating can pass through the crosslinked carboxy function dispersant in the presence of pigment and dispersant In some carboxyls prepare, preferably at a temperature of less than 100 DEG C and/or pH value is at least 6, this crosslinking is generally aqueous Carried out in medium, for example, in the mixture containing water and organic solvent.Described above for ink including water and organic molten The suitable mixture of agent.

Preferably, polymer encapsulating granules of pigments have less than 500nm Z average grain diameters, more preferably 10 to 400nm, particularly from 15 to 300nm.

Z average grain diameters can be determined by any mode, but preferred method is by can be fromOrThe photon correlation spectroscopy equipment bought.

For preparing the appropriate method for the granules of pigments that polymer is encapsulated in WO2006/064193 and WO2010/038071 In be described.Generally, the dispersant with carboxyl is adsorbed on pigment, and more then (but being not all of) carboxyl is handed over Connection, obtains wherein pigment and is for good and all captured the pigment dispersion in the dispersant of crosslinking.Such particle can be from FUJIFILM image producing colorants Co., Ltd is commercially-available.

Preferably, carboxyl-functional dispersant includes benzyl methacrylate.

It is preferred that carboxyl-functional dispersant be copolymer, it is unsaturated single that the copolymer includes one or more hydrophobic olefinics Body (preferably wherein at least half (weight) is benzyl methacrylate), the one or more parent with one or more carboxyls Aqueous ethylenically unsaturated monomer；There is the hydrophily of one or more hydrophilic nonionic groups with optional (some do not have) Ethylenically unsaturated monomer.

Especially preferred carboxyl-functional dispersant is the copolymer for including following components：

(i) 75 to 97 parts of one or more hydrophobic olefinics comprising at least 50 parts of benzyl methacrylate are unsaturated Monomer；

(ii) 3 to 25 parts of one or more hydrophily ethylenically unsaturated monomers with one or more carboxyls；And

(iii) 0 to 1 part of the hydrophily ethylenically unsaturated monomer with one or more hydrophilic nonionic groups；

Wherein described number is by weight.

Typically, the summation of (i), (II) and (III) number is added up as 100.

Preferably, unique hydrophobic olefinic unsaturated monomer in component (i) is benzyl methacrylate.

It is highly preferred that carboxyl-functional dispersant is the copolymer for including following components：

(i) 80 to 93 parts of one or more hydrophobic olefinics comprising at least 50 parts of benzyl methacrylate are unsaturated Monomer；

(ii) 7 to 20 parts of one or more hydrophily ethylenically unsaturated monomers with one or more carboxyls；

(iii) 0 to 1 part of the hydrophily ethylenically unsaturated monomer with hydrophilic nonionic group；

Wherein described number is by weight.

Typically, the summation of component (i), (II) and (III) is added up as 100.

Preferably, hydrophobic monomer does not have hydrophilic radical, either ionic or non-ionic.For example, they It is preferably without water-dispersible group.

Preferably, hydrophobic olefinic unsaturated monomer has the log P values of at least 1 calculating, more preferably from 1 to 6, especially It is 2 to 6.

Mannhold, R. and Dross.K. summary (Quant.Struct-Act.Relat.15,403-409,1996) are retouched State and how to have calculated Log P values.

It is preferred that hydrophobic olefinic unsaturated monomer be styrene monomer (for example, styrene and α-methylstyrene), virtue Race (methyl) acrylate (particularly benzyl (methyl) acrylate), C_1-30- alkyl (methyl) acrylate, butadiene, contain There is poly- (C_3-4) alkylen groups (methyl) acrylate, (methyl) acrylic acid containing alkylsiloxane base or fluoro-alkyl Ester and vinyl naphthalene.

Preferably, dispersant comprising 75 to 97 parts by weight of combined polymerization (more preferably 77 to 97 parts, particularly from 80 to 93 parts, most particularly 82 to 91 parts) component (i) repeat unit.

The dispersant of repeat unit comprising at least 50 parts of benzyls (methyl) acrylate monomer can be provided with good The pigment dispersion of the polymer encapsulating of stability well and good optical density.

Component (i) preferably includes at least 60 parts, more preferably at least 70 parts, the benzyl (first of especially at least 75 parts by weight Base) acrylate.Any or many of the above-mentioned hydrophobic monomer in addition to benzyl (methyl) acrylate can be passed through Plant to provide the remainder needed for the total preferred amounts for obtaining hydrophobic monomer.Preferably, benzyl (methyl) acrylate is first Base benzyl acrylate (rather than benzyl acrylate).

In a preferred embodiment, component (i) only includes benzyl (methyl) acrylate, more preferably only includes methyl-prop Olefin(e) acid benzyl ester.

Preferably, when in unneutralized (for example, free acid) form calculus, the monomer in component (II) has less than 1 The log P values of calculating, more preferably 0.99 to -2, particularly from 0.99 to 0, and most particularly 0.99 to 0.5.

Preferred hydrophily ethylenically unsaturated monomer for the component (ii) with one or more hydroxy-acid groups includes β-carboxyethyl acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, more preferably acrylic acid, especially methacrylic acid. Preferably, upon polymerization, these ethylenically unsaturated monomers provide only ionic group in dispersant.

In a preferred embodiment, component (ii) is or comprising methacrylic acid.

Preferably, the dispersant include the parts by weight of combined polymerization 3 to 25 (more preferably 3 to 23 parts, particularly 7 to 20 parts, especially 9 to 18 parts) component (ii) repeat unit.When component (ii) is included or during more preferably methacrylic acid, especially such as This.

For the purposes of the present invention, while having ion and the monomer of non-ionic hydrophilic group to be considered to belong to component (iii).Therefore, all ethylenically unsaturated monomers in component (ii) do not have hydrophilic nonionic group.

Preferably, the monomer in component (iii) has the log P values of the calculating less than 1, more preferably 0.99 to -2.

Preferably, component (iii) is less than 1 part, more preferably less than 0.5 part, most particularly especially less than 0.1 part, 0 part (i.e. in the absence of).By this way, dispersant is not contained from the hydrophily with one or more hydrophilic nonionic groups The repeat unit of monomer.

The example of hydrophilic nonionic group includes polyoxyethylene, polyacrylamide, PVP, hydroxyl official Can cellulose and polyvinyl alcohol.Most common ethylenically unsaturated monomer with Hydrophilic nonionic group is polyoxyethylene (methyl) acrylate.

There is the embodiment (components (III) of such as 1 parts by weight) of the repeat unit from component (iii) in dispersant In, then in one embodiment, the amount of component (III) is deducted from the preferred amounts of component (I).By this way, all components (i) it is still 100 that, the amount of (ii) and (III), which is added up,.Therefore, for there is the embodiment of the component (iii) of 1 parts by weight, the above The preferred amounts of the component (i) of expression will become 74 to 96 (75-1 to 97-1) parts by weight, more preferably 76 to 96 (77-1 to 97-1) Parts by weight, particularly 79 to 92 (80-1 to 93-1) parts by weight, most particularly 81 to 90 (82-1 to 91-1) parts by weight.Another Individual embodiment, can deduct the amount of component (iii) from component (ii) preferred amounts so that component (i), (ii) and (iii) It is 100 parts by weight again that the summation of amount, which is added up,.

The function of one or more of dispersant hydroxy-acid group is mainly with cross-linking agents and is subsequent polymer The granules of pigments of encapsulating provides the ability disperseed in water-based ink medium.When one or more hydroxy-acid groups are used for aqueous In medium during unique group of the granules of pigments of stable polymer encapsulating, it is preferable that for the carboxyl-reactive base in crosslinking agent Group's (such as epoxide group), the hydroxy-acid group with molar excess, to ensure after cross-linking reaction is completed, unreacted carboxylic acid Group is remaining.In one embodiment, carboxyl-reactive group (such as epoxy in the molal quantity and crosslinking agent of hydroxy-acid group Base) the ratio of molal quantity be preferably 10：1 to 1.1：1, more preferably 5：1 to 1.1：1, particularly preferably 3：1 to 1.1：1.

Dispersant optionally has other stable groups.The amount of the selection of stable group and these groups will be very big The property of aqueous medium is depended in degree.

In the embodiment that crosslinking agent has one or more oligomeric dispersing groups, dispersant, which preferably has, to be at least 125mg KOH/g acid number.

With cross-linking agents before, the acid number of dispersant be preferably 130 to 320mg KOH/g, more preferably 135 to 250mg KOH/g.We have found that, the dispersant with such acid number provides the granules of pigments of resulting polymer encapsulating, It shows good stability in water-based ink, and also has the enough carboxyls being used for then with cross-linking agents. Preferably, dispersant (before crosslinking) have 500 to 100000 number-average molecular weight, more preferably 1000 to 50000, especially 1000 to 35000.Molecular weight can be determined by gel permeation chromatography.

Dispersant need not be completely solvable in the liquid medium of the granules of pigments for preparing polymer encapsulating.Namely The solution for finishing all-transparent and non-scatter is not essential.Dispersant can be gathered into surfactant-based micella, be situated between in liquid Slight haze solution is produced in matter.Dispersant can be such so that the dispersant of some ratios be intended to be formed colloid or Micellar phase.Preferably, the dispersant produces uniform steady in the liquid medium of the granules of pigments for preparing polymer encapsulating Fixed dispersion, it does not settle or separated when standing.

Preferably, dispersant is substantially solvable in the liquid medium of the granules of pigments for preparing polymer encapsulating, produces Transparent or muddy solution.

It is preferred that atactic polymer dispersant tend to produce transparent composition, and with two or more sections not So preferred polymeric dispersant is intended to produce above-mentioned muddy composition in liquid medium.

Typically, dispersant is adsorbed onto on pigment before crosslinking, to form the metastable dispersion of granules of pigments. Then the dispersion is crosslinked to form the granules of pigments of polymer encapsulating using crosslinking agent.It is special that the pre-suction echos precondition The present invention and condensing method are distinguished, thus polymer or prepolymer (it is not dispersant) and granular solids, liquid medium Mixed with crosslinking agent, and the polymer that product is crosslinked only during or after crosslinking is deposited on granular solids.

In dispersant has at least embodiment of 125mg KOH/g acid number, crosslinking agent can be without oligomeric scattered Group, but preferably crosslinking agent has one or more oligomeric dispersing groups.

The granules of pigments of crosslinking agent increase polymer encapsulating with one or more oligomeric dispersing groups is in ink Stability.

Oligomeric dispersing group is preferably or including polyoxyalkylene, more preferably poly- C_2-4Oxyalkylene, particularly polyethylene glycol oxide. Polyalkylene oxide groups provide Steric stabilization, the stability of the granular solids to improve gained encapsulating.

Preferably, polyoxyalkylene contains 3 to 200 (more preferably 5 to 50, especially 5 to 20) oxyalkylenes and repeated Unit.

Crosslinking agent preferably has at least two epoxide groups.

Preferred crosslinking agent with two epoxide groups and the oligomeric dispersing group of zero be ethylene glycol diglycidylether, Resorcinolformaldehyde resin, neopentyl glycol diglycidyl ether, 1,6-HD diglycidyl ether, A Hydrogenated Bisphenol A A diglycidyl ethers and polybutadiene diglycidyl ether.

Preferred crosslinking agent with two epoxide groups and one or more oligomeric dispersing groups is the contracting of diethylene glycol two Water glycerin ether, polyethyleneglycol diglycidylether, DPG diglycidyl ether and polypropylene glycol diglycidyl ether.

Preferred crosslinking agent with three or more epoxide groups and the oligomeric dispersing group of zero is D-sorbite bunching Water glycerin ether, polyglycereol polyglycidyl ether, pentaerythrite polyglycidyl ether, diglycerol polyglycidyl ether, glycerine bunching Water glycerin ether and trimethylolpropane polyglycidyl ether.

In one embodiment, epoxy crosslinking agent has the oligomeric dispersing group of zero.

The example of oxetanes crosslinking agent includes 1,4 pairs of [(3- ethyl -3- oxetanylmethoxies methoxy)] benzene, 4, Double [(3- ethyl -3- oxetanylmethoxies) methoxyl group] benzene of 4'-, 1,4- it is double [(3- ethyl -3- oxetanylmethoxies) methoxyl group-benzene, 1, Double [(3- ethyl -3- oxetanylmethoxies) methoxyl group] biphenyl of double [(3- ethyl -3- oxetanylmethoxies) methoxyl group] benzene of 2-, 4,4- and 3,3', 5,5'- tetramethyl-[double (3- ethyl -3- oxetanylmethoxies) methoxyl groups of 4,4'-] biphenyl.

The example of carbodiimide cross-linker includes the crosslinking agent CX-300 from DSM NeoResins.Can also be such as US The carbodiimides in water with good dissolubility or dispersiveness is prepared described in 6124398 synthesis example 1 to 93 Crosslinking agent.

The example of isocyanate crosslinking includes IPDI, hexamethylene diisocyanate, toluene two Isocyanates, methyl diphenylene diisocyanate, methyldicyclohexyl diisocyanate, 2- methyl isophthalic acids, the isocyanic acid of 5- pentanes two Ester, 2,2,4- trimethyl -1,6- hexane diisocyanates and 1,12- dodecane diisocyanates, the isocyanic acids 11 of 1,11- bis- Alkane, the isocyanic acid dodecanes of 1,12- bis-, the isocyanato- hexanes of 2,2,4- and 2,4,4- trimethyls -1,6- two, the isocyanic acids of 1,3- bis- Cyclobutane, 4,4'- be double-and (cyclic isocyanate hexyl)-methane, hexamethylene diisocyanate, 1,2- be double-(isocyanatomethyl)- Cyclobutane, 1,3- and Isosorbide-5-Nitrae-bis- (isocyanatomethyls) hexamethylene, hexahydro -2,4- and/or -2,6- toluene di-isocyanate (TD.I)s, 1- are different Cyanic acid base -2- methyl isocyanates cyclopentane, 1- isocyanate group -3- isocyanatomethyl -3,5,5- trimethyl-cyclohexanes, 2, 4'- dicyclohexyl methyl hydride diisocyanates and 1- isocyanate groups -4 (3)-isocyanatomethyl -1- hexahydrotoluenes, tetramethyl - 1,3- and/or -1,4- XDIs, 1,3- and/or 1,4- phenylene vulcabonds, 2,4- and/or 2,6- first Phenylene diisocyanate, 2,4- and/or the diphenyl-methane diisocyanate of 4,4'- bis-, 1,5 naphthalene diisocyanate and p- benzene diformazan Group diisocyanate.Suitable diisocyanate is also understood to include those containing modification group, and modification group such as contracts Two ureas, urea diketone, isocyanuric acid ester, allophanate and/or carbodiimide-based, as long as they include two or more isocyanides Acid esters group.For isocyanates, liquid medium is preferably non-aqueous, although water can be resistant to enclosed type isocyanic acid sometimes Ester.

In a preferred embodiment, polyisocyanate crosslinking agent contains three isocyanate groups.Triisocyanate The convenient source of functional compound is the known isocyanate derivates of diisocyanate.The isocyanates of diisocyanate derives Thing can react to prepare by diisocyanate with suitable catalyst for trimerization one.Isocyanurate derivative is produced, its Include the isocyanuric acid ester core with the organic side chain by three isocyanate groups end-blockings.Some isocyanides of diisocyanate Urea acid ester derivant is commercially available.In a preferred embodiment, used isocyanuric acid ester is the isocyanide of isophorone two The isocyanuric acid ester of acid esters.In another preferred embodiment, using the isocyanuric acid ester of hexamethylene diisocyanate.

The example of N- methylol crosslinking agents includes dimethoxy dihydroxy ethylidene urea；N, N- dihydroxymethyl ethylamino first Acid esters；Tetramethylol acetylene diurea；Dihydroxymethyl alditol；Dihydroxymethyl ethylene urea；Dihydroxymethyl propylene urea；Dihydroxymethyl oneself two Sour acid amides；And their mixture including two or more.

The example of ketene imine crosslinking agent includes formula Ph₂C=C=N-C₆H₄- N=C=CPh₂Compound, wherein respectively Ph independently is optionally substituted phenyl.

The example of hydrazides crosslinking agent includes acid dihydrazide, the hydrazides of ethyl malonic acid two, amber acid dihydrazide, glutaric acid Two hydrazides, adipic dihydrazide, isophthalic dihydrazide, the hydrazides of oxalyl two and heptanedioyl hydrazine.

Commercially available high response oxazoline crosslinking agent can be from for example Japanese catalystTrade mark is bought Arrive.These include emulsion-type (for example, Epocross K-2000 are serial, such as K-2010E, K-2020E and K-2030E) and water Molten type (for example, Epocross WS are serial, such as WS-300, WS-500 and WS-700).

The example of aziridine crosslinker includes aziridine system polyaziridine, and (such as PZ-28 and PZ-33, are purchased from PolyAziridine LLC, Medford, NJ)；XC-103 trifunctionals aziridine, XC-105 polyfunctional aziridines and crosslinking agent XC-113 (is purchased from Shanghai Zealchem Co., Ltds, China)；Polyfunctional aziridines liquid cross-linker SaC-100 (is purchased from Shanghai UN Chemical Co., Ltd.s, China)；Aziridine crosslinker disclosed in WO 2009/120420；CX-100 (is purchased from DSM NeoResins)；Polyfunctional aziridines (are purchased from Lubrizol)；Trimethylolpropane tris (β-'-aziridino) Propionic ester, neopentyl glycol two (β-'-aziridino) propionic ester, glycerine three (β-'-aziridino) propionic ester, (β-nitrogen of pentaerythrite four Third piperidinyl) propionic ester, 4,4'- isopropylidenes xenol two (β-'-aziridino) propionic ester, 4,4'- methylene-di-phenols two (β- '-aziridino)；And their mixture including two or more.

Particularly preferred crosslinking agent is polyethyleneglycol diglycidylether (for example, with mean molecule quantity 526, being purchased from Aldrich) and/or trimethylolpropane polyglycidylether (for exampleEX-321, purchased from Nagase 140) Chemtex, epoxide equivalent is.

Preferably, the amount of component (a) be 0.75 to 4 part in the range of, more preferably 1 to 3 part.

The ink can include more than one styrene acrylic latex adhesive and/or Styrene butadiene latexes adhesive (component (b)).Emulsion binder can be different in terms of their characteristic, such as particle diameter, glass transformation temperature or molecular weight.

However, styrene acrylic latex adhesive and/or Styrene butadiene latexes adhesive are preferably styrene Acrylic latex binders or Styrene butadiene latexes adhesive.It is highly preferred that component (b) is viscous for styrene acrylic latex Mixture.

Preferably, the Tg of styrene acrylic latex adhesive is in the range of from -30 DEG C to 50 DEG C, more preferably from 0 DEG C in the range of 40 DEG C, particularly in the range of from 10 DEG C to 30 DEG C.

Preferably, the Tg of Styrene butadiene latexes adhesive is in the range of from 0 DEG C to 120 DEG C, more preferably from 10 DEG C in the range of 110 DEG C, especially in the range of from 50 DEG C to 90 DEG C.

Tg is determined by the differential scanning calorimetry of dry latex.Tg is taken from the scanning of reheating means of differential scanning calorimetry (i.e. Initial heating and cooling after) midrange.

Preferably, styrene acrylic latex has acid number in the range of 5 to 100mgKOH/g, more preferably from 30 To 70mgKOH/g.

Preferably, styrene acrylic latex adhesive and/or Styrene butadiene latexes adhesive are poly- by emulsion Close to prepare.

The molecular weight of styrene acrylic latex adhesive and Styrene butadiene latexes adhesive can be by this area Known method is controlled, for example, by using chain transfer agents (such as mercaptan) and/or by the case of emulsion polymerization Initiator concentration control, and/or pass through the heat time.Preferably, styrene acrylic latex adhesive and styrene fourth Diene emulsion binder has the molecular weight more than 20000 dalton, more preferably greater than 100000 dalton.It is particularly preferred that The molecular weight of styrene acrylic latex adhesive and Styrene butadiene latexes adhesive is more than 200000 to 500000 dongles .

Styrene-acrylonitrile copolymer acids emulsion binder and Styrene butadiene latexes adhesive can be unimodal, preferably have Average grain diameter less than 1000nm, more preferably less than 200nm, especially less than 150nm.Preferably, styrene acrylic latex The average grain diameter of adhesive and Styrene butadiene latexes adhesive is at least 20nm, more preferably at least 50nm.Therefore, benzene second Alkene acrylic latex binders and Styrene butadiene latexes adhesive preferably have flat in the range of from 20 to 200nm Equal particle diameter, more preferably in the range of from 50 to 150nm.Styrene-acrylonitrile copolymer acids emulsion binder and Styrene butadiene latexes The average grain diameter of adhesive can use photon correlation spectroscopy to determine.

Styrene acrylic latex adhesive and Styrene butadiene latexes adhesive can also show bimodal particle size distribution. This can be by mixing two or more latexes of different-grain diameter such as directly being produced by two-step polymerization reaction bimodal It is distributed to realize.When using bimodal particle size distribution, it is preferable that relatively low particle diameter peak is and higher in the range of 20-80nm Particle diameter peak is in the range of 100 to 500nm.It is further preferred that the ratio of two kinds of particle diameters is at least 2, more preferably at least 3, Most preferably at least 5.

Agilent HP1100 instruments (wherein THF is as eluent) and PL mixed gel C posts can be used to pass through gel Permeation chromatography determines styrene acrylic latex adhesive and Styrene butadiene latexes bonding relative to polystyrene standard The molecular weight of agent.

Once formed, it is preferable that for example, screening styrene acrylic latex adhesive and styrene fourth two by filter Alkene emulsion binder, to remove excessive particle using preceding, filter has an average pore size less than 3 μm, preferably 0.3 to 2 μm, especially 0.5 to 1.5 μm.Styrene third can be screened before, during or after forming ink being mixed with other components Olefin(e) acid class emulsion binder and Styrene butadiene latexes adhesive.

According to the present invention, commercially available styrene acrylic latex adhesive and styrene butadiene can be used in ink Emulsion binder.

Styrene acrylic latex adhesive and styrene butadiene breast commercially available from being used in the ink of the present invention The example of viscose binder includes what is supplied by Mallard Creek polymersThe styrene-acrylonitrile copolymer yogurt of scope Glue, particularly Rovene 6102, Rovene 6112 and Rovene 6103, and Styrene butadiene latexes, such as Rovene 5499 and Rovene 4111.

Component (b) is preferably in the range of 5 to 8 parts.

Component (c) is polyurethane latex adhesive.

Dispersions of polyurethanes is generally prepared by following steps：

(i) polymer diol (polyalcohol) (and optional other components that can be reacted with isocyanate groups) and two isocyanides Acid esters is reacted to produce prepolymer, then；

(ii) it is distributed in water, the chain extender reaction chain extension optionally by being reacted with water and/or with being present in aqueous phase Prepolymer；

Dispersion by the monomer (such as ionic group or non-ionic group) that is present in polyurethane or can pass through addition Surfactant stablize.

The Tg of polyurethane latex adhesive can be controlled by the selection of polyalcohol, diisocyanate and chain extender.Also may be used To control the Tg of polyurethane latex adhesive by mixing the latex with different Tg.

Preferably, the Tg of polyurethane latex adhesive is in the range of from -30 DEG C to 0 DEG C.

The weight average molecular weight of polyurethane is preferably>20000, more preferably>50000, most preferably>100000.

Polyurethane latex adhesive preferably has less than 1000nm average grain diameter, more preferably less than 200nm, particularly low In 150 nanometers.Preferably, the average grain diameter of emulsion binder is at least 20 nanometers, more preferably at least 50 nanometers.Therefore, it is newborn Viscose binder preferably has the average grain diameter in the range of from 20 to 200nm, more preferably in the range of 50 to 150nm. The average grain diameter of emulsion binder can use photon correlation spectroscopy to determine.

Commercially available polyurethane latex adhesive includes W835/177 and W835/397 from Incorez, from BASF 'sU4190 and from Lubrizol's20025F and Sancure2710.

The preferred existence range of component (c) is from 1 to 3 parts.As seen from the ink of the present invention, when being applied to low table During the substrate of face energy or for the durability of the printing under the conditions of moist and oiliness, emulsion binder is in terms of improved cohesive Play key effect.

As seen from the ink of the present invention, when being applied to the substrate of low-surface-energy or for moist and oiliness condition Under printing durability, emulsion binder (b) and (c) play key effect in terms of improved cohesive.

Component (d) is preferably ethylene glycol or triethylene glycol.

The existence range of component (d) is preferably 0.5 to 2.5 part, more preferably in the range of 0.75 to 2.0 part.

The existence range of component (e) is preferably 2.5 to 7.5 parts.

The existence range of component (f) is preferably 2 to 7.5 parts.

Any acetylenic surfactants may be used as component (g).However, 2,4,7,9- tetramethyl -5- decine -4,7- glycol With its ethylene oxide condensate and 2,5,8,11- tetramethyl -6- dodecyne -5,8- glycol and its ethylene oxide condensate It is preferred.

It is particularly preferred that acetylenic surfactants are 4,7,9 tetramethyl -5- decine -4,7- glycol or its oxirane Condensation product.It is particularly preferred that acetylenic surfactants are 4,7,9- tetramethyl -5- decine -4,7- glycol.Surfactant 2,4, 7,9- tetramethyl -5- decine -4,7- glycol and its ethylene oxide condensate are purchased from Air Products surfactant 'sScope.

It is preferred that surfactant 2,4,7,9- tetramethyl -5- decine -4,7- glycol purchased from Air ProductsThe analog of 440 or its ethoxylation465。

The mixture containing different surfaces activating agent can be used.

Component (g), which is present in composition, ranges preferably from 0.001 to 2.5 part, more preferably 0.01 to 1.5 part, especially It it is 0.05 to 1.0 part, more particularly in the scope from 0.1 to 0.5 part.

Surfactant is the key component in the ink of the present invention.In specific ink, surfactant and its dense The correct selection of degree is essential in terms of effective ink sprays the panel with nonwetting printhead.

It is essential that, the surfactant will not cause ink to bubble.

It is also contemplated that, ink is designed such that its nonwetting printhead panel (unused " non-wetting coating " processing). These panels can show the contact angle with water less than 90 °, or less than 80 °.Being specifically designed as non-wetted panel can With with the contact angle with water more than 90 °, sometimes more than 95 °, sometimes even greater than 100 °.

In order to realize these performances, it is desirable to which ink shows dynamic surface tension scope, i.e. its surface tension depends on table The face age.The surface tension on the surface newly created is high, but as surfactant or other surface reactive materials are migrated Decline to surface.Dynamic surface tension scope can be determined by being measured in aerotonometer.The surface tension of this measurement It is used as surface age or the function of bubble frequency.Preferably, the surface tension (γ (5)) measured in 5ms>35 dynes per centimeters, and The scope of the surface tension (γ (1000)) measured in 1000ms is 20 to 40 dynes per centimeters, γ (10)>γ(1000).It is optional Ground, the equilibrium surface tension of ink can be with being compared not comprising the equivalent ink prepared by surfactant.Preferably, do not have There are high at least 10 dynes per centimeters during surfactant in the equilibrium surface tension ratio of surfactant.

For component (h), (or the mixing of antimicrobial of any antimicrobial stable in ink can be used Thing).It is particularly preferred that antimicrobial is included from Lonza'sGXL can as the 1 of 20% living solution, 2- benzisothiazole-3-ketones and from Dow ChemicalDXN (2,6- dimethyl -1,3- dioxanes - 4- yl acetates).

Component (i) viscosity modifier is preferably chosen from being gathered by polyethers (such as polyethylene glycol and poly- (oxirane)), cellulose Compound (such as hydroxyethyl cellulose, hydroxypropyl cellulose and carboxymethyl cellulose), water-soluble polyester, the homopolymerization of 2- ethyl oxazolines Thing (such as poly- 2- ethyls -2- oxazolines), poly- (vinyl alcohol) and PVP and their mixture composition Group.

Component (i) is preferably PEG or poly- (oxirane).It is highly preferred that component (h) is polyethylene glycol, especially It is PEG 20000.

Preferably, the amount that component (i) is present in composition is 3 to 8 parts.

Ink preferably has the MFFT less than 65 DEG C, especially less than 60 DEG C.

MFFT be ink component component by coalescing to form the minimum temperature of film (such as during ink setting).

Equipment for measuring MFFT is commercially available, for example, MFT rod is purchased from Rhopoint Instruments (" MFFT rods 90 ").MFFT rods 90 include the temperature rod of the copper pressing plate with nickel plating, and the copper pressing plate of nickel plating has The thermograde that electronics applies.The equidistant sensor of 10 lower faces is provided to be measured along the transient temperature of rod.Needed for selection Temperature program(me), and allow instrument to reach thermal balance.Cube applicator or spreader can be used to apply wet test ink Track.Once ink setting, device shows MFFT.If for any reason, above-mentioned commercially available equipment does not work for ink A small amount of ink, can be placed in vessel and required by (for example, due to color of low content of latex and/or ink) Vessel of the heating containing ink 24 hours in temperature (such as 70 DEG C) are assessed, then wipe surface to assess film with glove finger Whether formed.If film has been formed, almost without printing ink transfer to glove finger, and if film is not formed, meeting Having ink to be significantly transferred to glove finger or the ink of drying can ftracture.

Desired MFFT can be realized by the appropriately combined of selective polymer latex and organic solvent.If ink MFFT is too high, then the amount that can increase agglomerated solvent and/or the polymer latex that can use relatively low Tg are so that ink MFFT reaches required scope.Therefore, in the ink design phase, depending on desired MFFT, in that case it can be decided that including more or The polymer latex of less agglomerated solvent and higher or lower Tg.

Typically, selection ink and substrate so that the MFFT of ink, which is less than, makes the temperature of substrate deformation, distortion or fusing. By this way, ink can form film at a temperature of substrate is not damaged in substrate.

In first preferred embodiment, when being measured using Brookfield SC4-18 under 150rpm, ink exists 32 DEG C of viscosity is in the range of from 10 to 14mPas.

In second preferred embodiment, when being measured using Brookfield SC4-18 under 150rpm, ink exists 32 DEG C of viscosity is in the range of 4 to 8mPas.

In first preferred embodiment, when being measured at 25 DEG C using Kruss K100 tensometers, the table of ink Face tension force is 20 to 65 dynes per centimeters, more preferably from 20 to 50 dynes per centimeters, particularly from 32 to 42 dynes per centimeters, more Especially from 34 to 38 dynes per centimeters.

In second preferred embodiment, when being measured at 25 DEG C using Kruss K100 tensometers, the table of ink Face tension force is 20 to 65 dynes per centimeters, more preferably from 20 to 50 dynes per centimeters, particularly from 30 to 40 dynes per centimeters.

Preferably, ink composite is filtered by filter, and filter has the average pore size less than 10 microns, more Preferably smaller than 5 microns, especially less than 1 micron.

Preferably, the pH value of the ink is in the range of 7.5 to 9.5.PH can be adjusted by suitable buffer solution.

Except component above-mentioned, ink composite can be optionally comprising one or more easers.Suitable for spray The preferred additive of black pad-ink is anti-scorch agent, rheology modifier, corrosion inhibitor and chelating agent.Preferably, own The total amount of such additive is not more than 10 parts by weight.These additives are added to one in ink and including component (j) Part, is added water in ink.

In a preferred embodiment, ink is included：

The self-dispersed pigment that 0.75 to 4 part of (a ')；

The styrene acrylic latex adhesive that 4 to 10 parts of (b ')；

The polyurethane latex adhesive that 1 to 3 part of (c ')；

The ethylene glycol that 0.5 to 2.5 part of (d ')；

The 2-Pyrrolidone that 2.5 to 7.5 parts of (e ')；

(f ') is 2 to 7.5 parts of glycerine；

2,4,7,9- tetramethyl -5- decine -4,7- the glycol that 0.05 to 1.0 part of (g ')；

The antimicrobial that 0.001 to 2 part of (h ')；

The viscosity modifier that 3 to 8 parts of (i ')；

The water of (j ') balance to 100 parts.

In second preferred embodiment, ink of the invention lacks glycol.That is, component (d) is zero.

Although the present invention has special value for nonabsorbable and/or temperature sensitive printed substrates, it also may be used For absorbability and/or not temperature sensitive printed substrates.For such substrate, ink of the invention and technique provide with Lower advantage：The printing under the lower temperature used in than existing process with good wear resistance property is provided, so that Reduce manufacturing cost.

The example of non-absorbent substrates includes polyester, polyurethane, phenoplasts, polyvinyl chloride, nylon, polymethylacrylic acid Methyl esters, polyethylene terephthalate, polypropylene, acrylonitrile-butadiene-styrene (ABS), makrolon, about 50% makrolon and Blend, polybutylene terepthatlate, rubber, glass, ceramics and the metal of about 50% acrylonitrile-butadiene-styrene (ABS).

In one embodiment, particularly preferably, ink of the invention is used to be printed upon substrate, and the substrate is comprising low close Spend polyethylene film.

In another preferred embodiment, ink is preferably used for printed substrates, and the substrate presses material comprising spunbond film layer Material, particularly polypropylene-base spunbond film laminate.

It is particularly preferred that ink is used to print nonwoven wipe, it is preferable that nonwoven wipe includes polypropylene, more Preferably include polypropylene-base spunbond film laminate.

It is possible if desired to pre-process (for example, being handled using plasma, corona discharge or surfactant) substrate with Strengthen adhesiveness of the ink to substrate.For example, substrate can be made roughening, or it can be coated with ink-absorbed coated layer.

At a temperature of in one embodiment, technique is additionally included at most 70 DEG C (more preferably at a temperature of at most 65 DEG C, Especially at a temperature of at most 60 DEG C) dry the ink for being applied to substrate.

The second aspect of the present invention provides a kind of InkJet printing processes, wherein will be according to the present invention by ink-jet printer First aspect ink print in substrate.Preferably, in the second aspect of the present invention, beaten using with ink recirculation The ink-jet printer of head is printed by ink print according to the first aspect of the invention to substrate.

The technique of the present invention can use any ink-jet printer with ink recirculation printhead.Preferably, this dozen Printing head has the ink recirculation raceway groove in ink supply system.The raceway groove allows fresh ink to can be used for spraying, and can To be that ink supply system is partly or even the specially designed raceway groove that extends below in nozzle plate.Preferably, ink is supplied Extend to system behind nozzle plate, because this allows to use more volatile ink ,/delay lines are restarted while not damaging For.The example of recycling behind nozzle plate is commercially available FUJIFILM Dimatix printheads, such asOr

The recycling printhead of preferred type is commonly equipped with holder heater and thermistor to control in the present invention Injection temperation processed.Preferably, in step (III), injection temperation is more than 30 DEG C.

Preferably, the droplet size of the ink applied by ink-jet printer is in the range of 1 to 100pl.

When the ink injection of first preferred embodiment as above described in step (I), applied by ink-jet printer The droplet size of ink is preferably in the range of 20 to 100pl, more preferably in the range of 20 to 40pl, particularly 25 To 35pl.

When the ink injection of the second preferred embodiment as above described in step (I), applied by ink-jet printer The droplet size of ink is preferably in the range of 1 to 20pl, more preferably in the range of 2 to 8pl,

The third aspect of the present invention is provided to be passed through such as the present invention using the ink as described in one aspect of the present invention The substrate of the InkJet printing processes printing of second aspect description.The substrate as described above and in the first aspect of the present invention is It is preferred that.

Therefore, in one embodiment, printed substrates preferably include low density polyethylene films.

In a second embodiment, printed substrates are preferably the substrate for including spunbond film laminate, particularly comprising poly- third The substrate of alkenyl spunbond film laminate.

It is highly preferred that in a second embodiment, printed substrates include nonwoven wipe, preferably comprising polypropylene, more Preferably include polypropylene-base spunbond film laminate.

According to the fourth aspect of the invention there is provided a kind of ink reservoir of ink-jet printer (for example, print cartridge or bigger Ink tank), it contains the ink as defined in the first aspect of the present invention.

The fifth aspect of the invention provides ink-jet printer, and it has as described in the second aspect of the present invention Recycling printhead and as described in the fourth aspect of the present invention accommodate ink ink-jet printer ink reservoir.

The sixth aspect of the present invention provides a kind of ink group, and it includes black ink, cyan ink, Yellow ink and magenta Ink, wherein ink as described above and be in the first aspect of the present invention preferably.Preferably, the pigment in black ink is Carbon black；Pigment in cyan ink is pigment blue 15:3；Pigment in Yellow ink is pigment yellow 74 (or pigment yellow 155)；With And the pigment in magenta ink is pigment red 122.Ink group can also contain blue ink and red ink.Preferably, it is blue Pigment in ink is that the pigment in pigment blue 60, and red ink is paratonere 254.

Example

The present invention will be shown by following example now, wherein all numbers are by weight, unless otherwise opposite Explanation.

The self-dispersed pigment used isAPD1000 black.Equal ink can be used It is prepared by APD1000 cyans, magenta, yellow and Huang LF, red and blueness.APD1000 pigment dispersions are purchased from FUJIFILM image producing colorants Co., Ltd.

440 and 465 be the acetylenic surfactants from Air Products.

6102 be the styrene acrylic dispersion from Mallard Creek Polymers. Rovene6102 Tg is 20 DEG C and acid number is 50mgKOH/g.

20025F is the aliphatic polyester based urethane polymeric dispersions from Lubrizol.

R-551 is the dispersions of polyurethanes from DSM.

1,2- benzisothiazole-3-ketones are from LonzaGXL (20% solution).

Example ink 1

Example ink 2

Component	The preparation (Wt%) of 100% activation
		Pro-Jet APD 1000 are black	2.00
Glycerine	3.75
		Ethylene glycol	1.25
2-Pyrrolidone 95%	5.00
		Surfynol 440	0.4
1,2- benzisothiazole-3-ketones	0.004
		Rovene 6102	5.50
NeoRez R-551	2.0
		PEG 20K	6.2
DI water	To 100

Property
		pH	8.6
Viscosity cP at 32 DEG C	12.85
		Surface tension D/cm	35.5

By from FUJIFILM Dimatix'sThe He of SG1024 recycling printhead prints examples ink 1 2。SG1024 recycling printhead is generally only used together with non-aqueous inks, because when together with water-based ink In use, its panel tends to " soak ", so as to negatively affect printer capability.

However, the printing of example ink does not have any problem.Printhead is taken pictures with JetXpert drop observers.Do not demonstrate,prove According to show any panel by the present invention any ink soak.

Compare ink example 1

Compare ink example 2

Component	The preparation (Wt%) of 100% activation
		Pro-Jet APD 1000 are black	2.00
Glycerine	3.75
		Ethylene glycol	1.25
2-Pyrrolidone 95%	5.00
		Surfynol 440	0.5
1,2- benzisothiazole-3-ketones	0.02
		Acrylic based emulsion	5.50
PEG 20K	5.75
		DI water	To 100

		Property
pH	8.4
		Viscosity cP at 32 DEG C	14.36
Surface tension D/cm	35.54

Compare ink example 3

Fastness to wet rubbing

Ink example 1 and 2 is printed on polyolefin film with being compared ink example 1 and 2.

Use the fastness to wet rubbing that printed product is assessed the step of the ASTM D5264 methods revised in F1571.

As a result it is shown in following, bigger number and reflects higher fastness to wet rubbing.

	Fastness to wet rubbing
		Ink 1	2.89
Ink 2	3.20
		Compare ink 1	1.24
Compare ink 2	2.2
		Compare ink 3	1.53

Obviously, ink of the invention is shown better than the fastness to wet rubbing for comparing ink.

Foam is tested

For resistance of the test ink to foaming, 2ml ink is introduced into disposable 12cm plastics testings pipe.Then sky is made Gas is by ink bubbling 2min, to allow the formation of foam.Then ink is stood into 2min, so that foam dissipates.In the foaming phase Between and foam dissipate during recorded with 30S time intervals the foam to be formed on ink height measurement.The formula of experiment one Three parts are carried out, and average result is shown in following table.

Obviously, ink of the invention shows foaming tendencies much lower compared with ink frequently, and any foam formed Dissipate faster.

Claims

1. a kind of ink, including：

(a) 0.5 to 5 part of self-dispersed pigment；

(c) 0.5 to 5 part of polyurethane latex adhesive；

(d) 0 to 5 part of glycol, the glycol is selected from what is be made up of ethylene glycol, diethylene glycol (DEG), propane diols, dipropylene glycol or triethylene glycol Group；

(e) 1 to 10 part of 2-Pyrrolidone；

(f) 1 to 15 part of glycerine；

(g) 0.1 to 3 part of acetylenic surfactants；

(h) 0.001 to 5 part of antimicrobial；

(i) 0 to 10 part of viscosity modifier；With

(j) water of balance to 100 parts.

2. ink according to claim 1, wherein, the self-dispersed pigment of component (a) is selected from by carbon black, pigment blue 15:3、 The group that pigment blue 60, pigment yellow 74, pigment yellow 155, paratonere 254 and pigment red 122 are constituted.

3. ink according to claim 1 or 2, wherein, the self-dispersed pigment in component (a) is included by two or more Carboxyl-functional dispersant of the epoxy groups cross-link around pigment core.

4. ink according to any one of the preceding claims, wherein, component (b) is styrene acrylic latex bonding Agent.

5. ink according to any one of the preceding claims, wherein, component (c) is in the range of 1 to 3.0 part.

6. ink according to any one of the preceding claims, wherein, component (d) is ethylene glycol.

7. ink according to any one of the preceding claims, wherein, the amount of component (e) is from 2.5 to 7.5 parts In the range of.

8. ink according to any one of the preceding claims, wherein, the amount of component (f) is in the model from 2 to 7.5 parts In enclosing.

9. ink according to any one of the preceding claims, wherein, component (g) be 2,4,7,9- tetramethyl -5- decine - 4,7- glycol.

10. ink according to any one of the preceding claims, wherein, component (i) is polyethylene glycol.

11. ink according to claim 1, including：

The self-dispersed pigment that 0.75 to 4 part of (a ')；

The styrene acrylic latex adhesive that 4 to 10 parts of (b ')；

The polyurethane latex adhesive that 1 to 3 part of (c ')；

The ethylene glycol that 0.5 to 2.5 part of (d ')；

The 2-Pyrrolidone that 2.5 to 7.5 parts of (e ')；

The glycerine that 2 to 7.5 parts of (f ')；

The antimicrobial that 0.001 to 2 part of (h ')；

The viscosity modifier that 3 to 8 parts of (i ')；

The water of (j ') balance to 100 parts.

12. a kind of InkJet printing processes, wherein, it will be wanted using the ink-jet printer with ink recirculation printhead according to right The ink print any one of 1 to 11 is sought in substrate.

13. the substrate printed by InkJet printing processes according to claim 12.

14. a kind of ink reservoir of ink-jet printer, accommodates the ink according to any one of claim 1 to 11.

15. a kind of ink-jet printer, the ink-jet with recycling printhead and receiving ink according to claim 14 is beaten The ink reservoir of print machine.