CN1205731A - Water based inks containing near infrared fluorophores - Google Patents
Water based inks containing near infrared fluorophores Download PDFInfo
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- CN1205731A CN1205731A CN 96199105 CN96199105A CN1205731A CN 1205731 A CN1205731 A CN 1205731A CN 96199105 CN96199105 CN 96199105 CN 96199105 A CN96199105 A CN 96199105A CN 1205731 A CN1205731 A CN 1205731A
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Abstract
The present invention provides inks which contain a near infrared fluorophoric compound incorporated into a water-dissipatible polyester backbone. The inks of the present invention are preferably colorless or 'invisible' but could be made slightly colored if desirable. Specifically, the inks of the present invention comprise: A. between about 1 and 10 weight percent of at least one water-dissipatable polyester having from about 0.1 ppm by weight to about 10% by weight of a thermally stable near infrared fluorophoric compound copolymerized therein; B. between about 5 and 75 weight percent of at least aliphatic humectant; C. between about 0 and 15 weight percent of at least one lower aliphatic alcohol of no more than 3 carbon atoms; D. water and optionally up to about 2 weight percent of one or more additives; wherein the weight percentages of components A-D equal 100%.
Description
Invention field
The present invention relates to be applicable to that by dripping (DOD) and the aqueous ink prescription of Method of printing spray ink Printing continuously as required this ink formulations contains and has near-infrared fluorescent and roll into a ball copolymerization sulfopolyester/acid amides therein.
Background of invention
Provide on product surface that people's eyesight in fact invisiblely is used to discern, identifies, the clear mark of classification etc. is in demand.US5093147; US5336714 discloses and has used some near infrared fluorescent compound, this compound visible-range 400-700 millimicron (nm) have minimum radiating photoabsorption and near infrared range 700-900 millimicron (nm) thus having strong photoabsorption produces than excitation wavelength long wavelength's fluorescent radiation more with fluorescence simultaneously., openly be not applicable to the aqueous ink prescription of spray ink Printing, and the stability of daylight/ultraviolet (UV) light be not enough to allow to be applicable to the needed actual mark speed of clear mark by the mark of these compound formation.
The characteristics of the polymeric composition that uses in US5336714 are near-infrared fluorescent group (NIRF) by copolymerization therein, therefore cannot be extracted, ooze out, distil or leach from this polymeric composition.The characteristics of phthalocyanine of wherein mentioning and naphthalene cyanines are that they provide than the known cyanine laser dyes that uses and have improved UV light stability in US5093147., US5093147 does not provide any help aspect the water-based inks of spray ink Printing using this polymeric composition that contains copolymerization NIRF compound preparation to be applicable to.
US4540595 provides a kind of to be had fluorescence and is used for the tab file printing ink of (for example being used for the bank check of identification automatically) near infrared.Employed dyestuff is blueness to be given be labeled thing and be that (for example nitric acid 3, two (the diethylamino) phenoxazine of 7-for invisible phenoxazine.
Used some inorganic rare earth compound (neodymium (Nd), erbium (Er) and yttrium (Yb) are representative) so that can in infrared light, give data card (US4202491) by activated fluorescence mark.Be easy to stop up the printing ink nozzle by the printing ink of these soluble rare earth metals preparations and cause that poor printing starts, therefore usually can not be practical.
In US5093147, disclose and used some known polymethine (cyanine) laser dyes to be used for cannot see the printing ink of mark printing Infrared fluorescence on the product surface.Therefore, these used dyestuffs have the shortcoming of fading or decomposing when the short period of time is exposed to UV-light, make this marking method variation.
Known (US3630941) some 16,17-dialkoxy violanthrone (being also referred to as dibenzanthrone) is not although they have fluorescence when solid state, is useful as the Infrared fluorescence mark when it is dissolved in the various substrates.These macromolecular compounds are water-fast basically, and are therefore of no use for the water-based inks prescription that is used for spray ink Printing.In addition, these compounds have significant absorption to the light that is lower than 700 millimicrons of wavelength, therefore can not provide invisible mark usually.
Japanese Laid-Open Patent Application 03-79683 discloses the ink formulations that contains infrared absorption naphthalene cyanine compound, and this prescription is useful to printing bar code and identification document with tamperproof and forgery.Various fusible waxes and thermoplastic resin are used as vehicle combining with pure and mild aromatic hydrocarbon so that prepare in the non-aqueous ink.This high molecular naphthalene cyanine compound is water-fast basically and is otiose for the aqueous ink that preparation is used for direct spray ink Printing.Fluorescence when the marking method of mentioning in this application does not utilize these naphthalene cyanines to be exposed to ir radiation, but only rely on the absorption of ir radiation.
US5336714 discloses the dispersible sulfopolyester of 20-35% (weight) water and has been dispersed in aqueous coating composition in the water (65-80% (weight)), and this polyester has 0.1ppm-10% (weight) copolymerization heat-staple near infrared fluorescent compound wherein.Disclosed this ink formulations (embodiment 7) is applicable to lower link and applies substrate (for example paper), but is not suitable for spray ink Printing, because stop up or adhere to nozzle.
The description of invention
The present invention relates to be applicable to the aqueous ink compositions of spray ink Printing, comprising:
A.1-10% the dispersible polyester of at least a water of (weight), it comprises:
(ⅰ) monomer residue of at least a dicarboxylic acid;
(ⅱ) in the total amount of all acid, hydroxyl and amino equivalent, 4-25%'s (mole) contains the monomer residue that at least one key is linked at least a double functional group's sulfomonomer of the sulfonation group on the aromatic nucleus, and wherein functional group is hydroxyl, carboxyl, carboxylicesters or amino;
(ⅲ) monomer residue of at least a dibasic alcohol or dibasic alcohol and two amine mixt; Randomly,
(ⅳ) at least a monomer residue that is selected from the difunctional monomer reactant of hydroxycarboxylic acid, aminocarboxylic acid and aminoalkanol;
Condition is: the group that at least 20% key connects this monomeric unit is an ester bond; The dispersible polyester of described water has 0.1ppm-10% (weight) copolymerization heat-staple near infrared fluorescent compound therein;
B.5-75% at least a tackiness agent of (weight);
C.0-15% the rudimentary aliphatic alcohol of at least a no more than 3 carbon atoms of (weight);
D. water and optional one or more additives that are up to 2% (weight);
Wherein this weight percentage is based on the total weight of component A-D.
In preferred embodiments, component A is the dispersible sulfo group ester of water, and component (ⅲ) comprising: (a) in the total mole of dibasic alcohol monomer residue, and at least 15% formula H (OCH
2CH
2)
nThe dibasic alcohol of OH, wherein n is 2-20, or (b) in the total mole of dibasic alcohol monomer residue or dibasic alcohol and diamines residue, the formula H (OCH of 0.1-15%
2CH
2)
nPoly-(ethylene glycol) of OH, wherein n is 2-500, condition is: the molecular fraction of above-mentioned residue and n value are inversely proportional to.
The dispersible polyester of this water is that the particle diameter that can form electrostatic stabilization is the 200-800A ° of any polyester of colloidal.This polyester is the dispersible sulfopolyester/acid amides of employed water among the US5336714 preferably.
Composition of the present invention can be used for the various printers that can use water-based inks.
For example, comprise for drip the useful ink composite of (DOD) spray ink Printing as required by the piezoelectricity pulse method:
A.1-10% the dispersible polyester of described at least a water of (weight), this polyester has 0.1ppm-10% (weight) copolymerization heat-staple near infrared fluorescent compound therein;
B.45-75% the described at least a tackiness agent or the wetting agent of (weight);
C.2-15% at least a lower alcohol of (weight);
D.0.01-0.50% at least a corrosion inhibitor of (weight);
E.0.01-0.30% at least a biocides of (weight);
F. water, wherein this weight percentage is according to the total weight of component A-F.
Another comprises for drip the useful especially preferred ink compositions of (DOD) spray ink Printing as required by so-called foaming injection method:
A.1-10% the dispersible polyester of described at least a water of (weight), this polyester has 0.1ppm-10% (weight) copolymerization heat-staple near infrared fluorescent compound therein;
B.20-60% the described at least a wetting agent of (weight);
C.0.50-1.5% at least a tensio-active agent of (weight);
D.0.01-0.5% at least a corrosion inhibitor of (weight);
E.0.01-0.3% at least a biocides of (weight);
F. water, wherein this weight percentage is according to the total weight of component A-F.
Print useful especially preferred ink compositions and comprise for using Scitex ink-jet imaging system (Scitex Digital Printing, Inc., Dayton, Ohio 45420-4099) continous inkjet:
A.1-10% the dispersible polyester of described at least a water of (weight), this polyester has 0.1ppm-10% (weight) copolymerization heat-staple near infrared fluorescent compound therein;
B.4-8% the described at least a wetting agent of (weight);
C.0.35-0.65% at least a tensio-active agent of (weight);
D.0.75-1.25% at least a defoamer of (weight);
E.0.01-0.50% at least a corrosion inhibitor of (weight);
F.0.01-0.3% at least a biocides of (weight);
G. water, wherein the A-G component weight percentage equals 100%.
At last, the preferred ink compositions that is used for single nozzle continous inkjet printers (for example Codebox 2, and by Amjet, DominoAmjet, Inc., Gurnee, IL 60031 provides) comprises:
A.1-10% the dispersible polyester of at least a water of (weight), this polyester has 0.1ppm-10% (weight) copolymerization heat-staple near infrared fluorescent compound therein;
B.30-50% at least a wetting agent of (weight);
C.5-15% the described at least a lower aliphatic alcohols of (weight);
D.0.01-0.50% at least a corrosion inhibitor of (weight);
E.0.01-0.30% at least a biocides of (weight);
F. water, wherein the weight percentage of component A-F equals 100%.
The polyester of component A is sulfopolyester and/or sulfopolyester acid amides preferably.The dispersible polyester of this water that does not wherein mix near infrared fluorescent compound is described in U.S. Patent number 3734874; 3779993; 3828010; 3546008; 4233196; In 4435220.
Useful preferred near infrared fluorescent compound is selected from phthalocyanine, naphthalene cyanines and squaraines (derivative of squaric acid) and corresponding to the compound of following formula II, III and IV in the present invention practice:
The wherein phthalocyanine of Pc and Nc expression II a and III a and naphthalene cyanines part,
Phthalocyanine 2,3-naphthalene cyanines
Respectively, its covalently key link on hydrogen or various metal, halo metal, organometallic group and the oxidized metal, comprise AlCl, AlBr, AlF, AlOH, AlOR
5, AlSR
5, Fe, Ge (OR
6)
2, GaCl, GaBr, GaF, GaOR
5, GaSR
6, Pb, InCl, Mg, Mn, SiCl
2, SiF
2, SnCl
2, Sn (OR
6)
2, Si (OR
6)
2, Sn (SR
6)
2, Si (SR
6)
2And Zn,
R wherein
5And R
6Be selected from: the group of hydrogen, alkyl, aryl, aroyl, heteroaryl, lower alkane acyl group, trifluoroacetyl group, following formula:
R
7, R
8And R
9Be selected from independently of one another: the phenyl that alkyl, phenyl or low alkyl group, lower alkoxy or halogen replace;
X is selected from: oxygen, sulphur, selenium, tellurium or formula N-R
10Group, R wherein
10Be hydrogen, cycloalkyl, alkyl, acyl group, alkyl sulphonyl or aryl, perhaps R
10Form aliphatics or aromatic ring with the nitrogen-atoms that is connected them together with R;
Y is selected from: alkyl, aryl, halogen or hydrogen;
R is selected from: unsubstituted or the alkyl, alkenyl, alkynyl group, the C that replace
3-C
8Cycloalkyl, aryl, heteroaryl, alkylidene group
Or alkylidene group
Or
-(X-R)
mBe alkyl sulfonyl-amino, arlysulfonylamino or the group that is selected from following formula :-X (C
2H
4O)
zR
1,
R wherein
1Be hydrogen or definition R as above; Z is the integer of 1-4; Or 2-(X-R)
mCan form the divalent substituent of following formula together:
X wherein
1Be selected from independently of one another :-O-,-S-or-N-R
10And A is selected from: ethylidene, propylidene, trimethylene and use C
1-C
4Alkyl, C
1-C
4The above group of alkoxyl group, aryl and cycloalkyl substituted, 1,2-phenylene and contain 1-3 and be selected from C
1-C
4Alkyl, C
1-C
4Alkoxy or halogen is substituent 1, the 2-phenylene;
R
1And R
2Be selected from independently of one another: hydrogen, low alkyl group, lower alkoxy, halogen, aryloxy, lower alkylthio, arylthio, low alkyl group alkylsulfonyl, aryl sulfonyl, low alkyl group sulfuryl amino, arlysulfonylamino, naphthene sulfamide base amino, carboxyl, the unsubstituted and formamyl that replaces and sulfamyl, elementary alkoxy carbonyl, hydroxyl, lower alkanoyloxy,
R
3And R
4Be selected from independently of one another: hydrogen, low alkyl group, alkenyl or aryl; N is the integer of 0-12; n
1Be the integer of 0-24, m is the integer of 4-16; m
1Be the integer of 0-16, condition is: n+m and n
1+ m
1Be respectively 16 and 24.
In the preferred embodiment of this respect of the present invention, m is 4-12; m
1Be 0-8; Condition is: at substituting group (Y) n, (Y) n
1The m of (-X-R)
1Definition in, as n, n
1And m
1Be respectively 0 o'clock, these substituting groups do not exist.Substituting group (X-R) m and (Y) n be present on the peripheral carbon atom of compound ii a, promptly 1,2,3,4,8,9,10,11,15,16,17,18,22,23, on 24,25, and substituting group (X-R) m
1(Y) n
1Be present on the peripheral carbon atom of compound III, promptly 1,2,3,4,5,9,10,11,12,13,14,18,19,20,21,22,23,27,28,29,30,31, on 32 and 36.
This near infrared fluorescent compound preferably covalently key is linked on the part that is selected from following group: AlCl, AlBr, AlF, AlOH, AlOR
5, AlSR
5, Ge (OR
6)
2, GaCl, GaBr, GaF, GaOR
5, GaSR
6, Mg, SiCl
2, SiF
2, SnCl
2, Sn (OR
6)
2, Si (OR
6)
2, Sn (SR
6)
2, Si (SR
6)
2And Zn.
Phthalocyanine and naphthalene cyanines are preferred near-infrared fluorescent groups, are especially needing the place of stability needing to UV light or daylight.
In above-mentioned definition, term " alkyl " is used for representing containing the hydrocarbyl group of the straight or branched of 1-12 carbon atom.
In term lower alkyl, lower alkoxy, lower alkylthio, elementary alkoxy carbonyl, in lower alkane acyl group and the lower alkane acyloxy, the moieties of this group contains 1-6 carbon atom and can be straight or branched.
Term " cycloalkyl " is used for expression and contains 3-8 carbon atom, preferably the annular aliphatic hydrocarbyl group of 5-7 carbon atom.
The alkyl of above-mentioned definition group and low alkyl group part can contain another kind of or multiple hydroxyl, halogen, carboxyl, cyano group, the C of being selected from
1-C
4-alkoxyl group, aryl, C
1-C
4-alkylthio, arylthio, aryloxy, C
1-C
4-alkoxy carbonyl or C
1-C
4The group of-alkanoyloxy.
Term " aryl " comprises the carbocyclic ring aromatic group that contains 6-18 carbon atom, preferred phenyl and naphthyl and be selected from such groups that following substituting group replaces: low alkyl group, lower alkoxy, halogen, low alkyl group sulfenyl, N (low alkyl group) by one or more
2, trifluoromethyl, carboxyl, elementary alkoxy carbonyl, hydroxyl, lower alkane acyl amino, low alkyl group sulfuryl amino, arlysulfonylamino, naphthene sulfamide base amino, lower alkane acyloxy, cyano group, phenyl, phenyl sulfenyl and phenoxy group.
Term " heteroaryl " is used for representing list or the assorted aromatic group of dicyclo, and it contains at least one and is selected from oxygen, sulphur and nitrogen heteroatom or these heteroatomic combinations.The example of suitable heteroaryl comprises: thiazolyl, benzothiazolyl, pyrazolyl, pyrryl, thienyl, furyl, thiadiazolyl group, oxadiazole base, benzoxazolyl, benzimidazolyl-, pyridyl, pyrimidyl and triazolyl.These heteroaryls can contain the substituting group identical substituting group possible with the aryl of listing above.Term " triazole " also comprises following structure V and its blended isomer,
R wherein
11Be hydrogen or be selected from low alkyl group and be selected from the low alkyl group that hydroxyl, halogen, carboxyl, lower alkoxy, aryl, cyano group, cycloalkyl, lower alkane acyloxy or elementary alkoxy carbonyl replace with 1 or 2.
Term " alkenyl and alkynyl group " is used for representing to have 3-8 carbon atom and containing at least 1 carbon-to-carbon double bond respectively and the aliphatic hydrocarbon moiety of 1 carbon-to-carbon triple bond.
Term " halogen " generally includes bromine, chlorine, fluorine and iodine.
Term " alkyl of replacement " is used for representing to contain 1-12 carbon atom and contain 1 or 2 to be selected from hydroxyl, halogen, carboxyl, cyano group, C
1-C
4Alkoxyl group, aryl, C
1-C
4Alkyl sulfenyl, artyl sulfo, aryloxy, C
1-C
4Alkoxy carbonyl or C
1-C
4The substituent straight or branched alkyl of alkanoyloxy.
Term " formamyl of replacement " is used for expression and has formula-CONR
12R
13Group, R wherein
12And R
13Be selected from the alkyl, alkenyl, alkynyl group, cycloalkyl, aryl or the heteroaryl that do not replace or replace.
Term " sulphonamide of replacement " is used for expression and has formula-SO
2NR
12R
13Group, R wherein
12And R
13As top definition.
The C of term " alkylidene group " expression divalence
1-C
12The aliphatic hydrocarbon part, itself or straight chain or side chain, or unsubstituted or be selected from one or more that lower alkoxy, halogen, aryl or aryloxy replace.
Term " acyl group " expression R
0The group of C (O)-O-, wherein R
0C preferably
1-C
10Moieties.Term " alkyl sulphonyl " expression R
0SO
2-group, R wherein
0As be used for the definition of acyl group.
Preferably-the X-R group comprise list in below the table I those groups.
Table 1 is typical-X-R group-X-R-X-R-OCH
3 
-OC
4H
9-n
-OC (CH
3)
3 
-OC
12H
25-n
-SCH
3 -SC
2H
4OH
-SC
8H
17-n
Table 1 (continuing) is typical-X-R group-X-R-X-R-OCH
2CH (C
2H
5) C
4H
9-n
-OCH
2CH=CH
2 
-OCH
2CH=CH-CH
3 
-SCH
2C
6H
5 -SCH
2CH (OH) CH
2OH-OCH
2C
6H
4-4-COOH-OCH
2C ≡ CH-OC
6H
4-4-CH
2COOH-N (C
2H
5)
2-OCH
2CH
2CO
2CH
3-NHC
6H
5-OCH
2CH
2OCOCH
3-N (CH
3) C
6H
5-O-C
6F
5-N (C
2H
4OH)
2-OC
6H
4-4-Cl-NHC
6H
11
Table 1 (continuing) is typical-X-R group-X-R-X-R
-OC
6H
5-O (CH
2CH
2O)
2H-OC
6H
4-4-COOH-S (CH
2CH
2O)
2H-SC
6H
4-4-COOH-O (CH
2CH
2O)
4H-OC
6H
3-3,5-diCOOH-O (CH
2CH
2O)
3CH
3-OC
6H
3-3,5-diCO
2CH
3-O (CH
2CH
2O)
2C
6H
5-SC
6H
4-2-COOH-NH (CH
2CH
2O)
2H-SC
6H
4-3-CO
2CH
3
Table 1 (continuing) is typical-X-R group-X-R-X-R-OC
6H
4-4-C
2H
4OH-OC
6H
4-4-OC
2H
4OH
In the compound, should be realized that in the above: this structure must have at least one pet reaction group, and this polymeric composition neutralization connects by the covalent linkage key so that allow this compound to mix into.
The water dispersible polymers that near infrared fluorescent compound is mixed wherein is not described in U.S. Patent number 3734874; 3779993; 3828010; 3546008; 4233196; In 4435220, these documents are incorporated herein by reference.
Polymkeric substance of the present invention is that water is dispersible mostly, because they form the colloid of electrostatic stabilization when it mixes with water.This colloidal particle size is formed variation according to polymkeric substance, but shows that by optical diffraction research and transmission type microscope (to the research of fresh film) its diameter is 200-800A ° basically.This moisture colloidal dispersion demonstrates minimum solid material precipitation in time 0.1-99.9 ℃ temperature range, because the relation between pellet density and the viscosity (being very similar to water when concentration is lower than 30%) is such, that is, the heat energy of representing with pedesis is enough to keep particle suspension in water.
When the 0.25g polymer determination in the solvent of being made up of 60 weight part phenol and 40 weight part tetrachloroethane with every 100ml at 25 ℃, the logarithmic viscosity number of the dispersible polyester of this water is 0.1dL/g at least, preferred 0.28-0.38dL/g.
The dispersible linear polymer of water that contains sulfonate comprises: polyester comprises polyester-amides, its repetition by (1) one or more dicarboxylic acid and (2) one or more dibasic alcohol or one or more dibasic alcohol and the combination of one or more diamines, alternately residue is formed, wherein in above-mentioned definition, molecular fraction is by 100% (mole) dicarboxylic acid residue and 100% (mole) dibasic alcohol or dibasic alcohol and diamines residue.In addition, this polymkeric substance can comprise having for example residue of hydroxycarboxylic acid, aminocarboxylic acid and/or aminoalkanol of mixed functionality monomer.Therefore this near-infrared fluorescent (NIRF) compound can be incorporated in this polyester, as long as this NIRF has 1, or preferred 2 pet reaction groups (for example hydroxyl, carboxyl etc.) exist just.
The derivative that the residue of component (ⅰ) can form ester from one or more dicarboxylic acid or its is dialkyl, two (hydroxyalkyl) ester, chloride of acid for example, or acid anhydrides obtains in some cases.The sulfonate groups of component (ⅱ) can be for example lithium, potassium or preferred sodium group of alkali metal sulfonate, perhaps ammonium or replacement ammonium sulfonate.
The logarithmic viscosity number of preferred water dispersible polymers is 0.28-0.38dL/g and is made up of following component:
(ⅰ) diacid monomer residue comprises the m-phthalic acid monomer residue of 75-84% (mole) and the 5-sodium sulfoisophthalic acid monomer residue of 16-25% (mole); With
(ⅱ) residue of dihydric alcohol comprises 45-60% (mole) Diethylene Glycol monomer residue and 40-55% (mole) ethylene glycol, 1,4 cyclohexane dimethanol monomer residue or its mixture.
The object lesson of these water dispersible polymers is to obtain with pellet shaped formula (EASTMAN AQ 29S polymkeric substance, EASTMAN 38S polymkeric substance and EASTMAN 55S polymkeric substance) with aqueous dispersions form (EASTMAN AQ 29D polymkeric substance, EASTMAN38D polymkeric substance and EASTMAN 55D polymkeric substance) from Eastman ChemicalCompany.Owing to have 5-sodium sulfoisophthalic acid monomer residue, be dispersed in the water so these polyester demonstrate.
Preferably, the top dispersible polyester of water contains some poly-(ethylene glycol) to help its water dispersible.When using some poly-(ethylene glycol), the content of sulfomonomer can reduce, and this helps to prepare flexibly this polyester.
The water-dispersible of this polyester is relevant with the molecular fraction of weight percentage of gathering (ethylene glycol) and sulfomonomer.Therefore, if one of them content is relatively low, another just should be higher relatively so that keep enough dispersivenesses so.
When initial reaction is reinforced, do not need to exist poly-(ethylene glycol), because poly-(ethylene glycol) can be from the degradation production original place forms and be impregnated in into polyester chain.What for example, people knew is: form Diethylene Glycol on such ground, reaction Central Plains.
In a preferred form of the invention, this polyester contains formula H-(OCH
2-CH
2)
nPoly-(ethylene glycol) repeating unit of-OH, wherein n is the integer of 2-500.The n value is 2-20 preferably.If you are using, the molecular fraction of regulating the n value in this polyester like this and gathering (ethylene glycol) makes that poly-(ethylene glycol) molecular fraction and the amount of the n in described scope in described scope is inversely proportional to.Like this, when this molecular fraction was high, the n value was just low.On the other hand, if this molecular fraction is low, the n value is just high so.Therefore, the weight percentage (product of molecular fraction and molecular weight) of obviously poly-(ethylene glycol) is an important consideration condition, because the water dispersible of this copolyesters reduces with the weight percentage of poly-(ethylene glycol) in this copolymer esters.For example, if the weight of poly-(ethylene glycol) is too low, the water dispersible of this copolyesters may be not enough so.In addition, preferred weight percentage of regulating poly-(ethylene glycol) like this makes the molecular fraction of it and difunctional sulfomonomer be inversely proportional to, because the water dispersible of this copolyesters is the function of sulfomonomer molecular fraction and polyoxyethylene glycol weight percentage.
The example of suitable poly-(ethylene glycol) comprises relative high molecular weight polyethylene glycol, its some can title CARBOWAX, buy by Union Carbide.Diethylene Glycol also is specially suitable.
Other the useful dibasic alcohol that is used to prepare copolyesters comprises: aliphatic, alicyclic and arylalkyl dibasic alcohol.The example of these dibasic alcohol comprises: ethylene glycol; Propylene glycol; 1, ammediol; 2,4-dimethyl-2-ethyl hexane-1,3-glycol; 2; 2-ethyl-2-butyl-1, ammediol; 2-ethyl-2-isobutyl--1, ammediol; 1,3 butylene glycol; 1, the 4-butyleneglycol; 1, the 5-pentanediol; 1, the 6-hexylene glycol; 2,2,4-trimethylammonium-1,6-hexylene glycol; Thiodiethanol; 1, the 2-cyclohexanedimethanol; 1, the 3-cyclohexanedimethanol; 1,4 cyclohexane dimethanol; 2,2,4,4-tetramethyl--1,3-cyclobutanediol; With right-Ya Xylene glycol.
The dicarboxylic acid component of this polyester is preferably from two or more mixture of: aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, aromatic dicarboxilic acid or these acid.The example of such dicarboxylic acid comprises: succsinic acid; Pentanedioic acid; Hexanodioic acid; Nonane diacid; Sebacic acid; 1, the 4-cyclohexane dicarboxylic acid; Phthalic acid; Terephthalic acid; M-phthalic acid.Terephthalic acid and m-phthalic acid are preferably as the carboxyl acid component of this polyester.
Should be appreciated that and in term " dicarboxylic acid ", comprise corresponding acid anhydrides, ester and the chloride of acid that uses these acid.
The difunctional. sulfomonomer component of this polyester can contain the ester of metal sulfonate salt group, the hydroxycarboxylic acid that contains the dibasic alcohol of metal sulfonate salt group or contain metal sulfonate salt group for dicarboxylic acid or its.The metal ion of this sulfonate can be Na
-, Li
+, K
+Deng.When using the monovalent base metal ion, the polyester that obtains is not easy with the cold water dispersion and is easier to disperse with hot water.When using divalence or trivalent metal ion, the polyester that obtains generally is not easy to disperse with cold water, but is easier to be dispersed in the hot water.Can prepare this polyester like this, for example use sulfonate sodium and latex and by ion-exchange with this ion of different ion exchanges, change the characteristic of polymkeric substance thus.This difunctional monomer component is also referred to as difunctional. sulfomonomer and further describes hereinafter.
Favourable difunctional. sulfomonomer component is wherein sulfonate groups to be connected to aromatic acid to examine on benzene for example, naphthalene, biphenyl, oxygen biphenyl, alkylsulfonyl biphenyl or the methylene radical biphenyl nuclear those.By using sulfo group phthalic acid, sulfo group terephthalic acid, sulfoisophthalic acid, 4-sulfo group naphthalene-2,7-dicarboxylic acid and their ester have obtained preferred result.
When this difunctional. sulfomonomer component is that 5-sodium sulfo group-m-phthalic acid or its ester and this dibasic alcohol have obtained excellent especially result when being the mixture of ethylene glycol or 1,4 cyclohexane dimethanol and Diethylene Glycol.
B component is wetting agent or tackiness agent, comprises water miscible and has enough viscosity so that printer and substrate any wetting agent or tackiness agent with printing ink required character to be provided.The example of suitable wetting agent and tackiness agent comprises: ethylene glycol, propylene glycol, butyleneglycol, glycerol, M
nFormula H-(OCH between 200-10000
2-CH
2)
nThe polyoxyethylene glycol of-OH; M
nPoly-(ethylene glycol) methyl ether for 250-5000; Polyvinyl alcohol, polyvinyl pyridine and polyvinylpyrrolidone and its mixture.Described wetting agent preferably from: ethylene glycol, propylene glycol, butyleneglycol, glycerol, wherein n is the formula H-(OCH of 2-6
2-CH
2)
nThe polyoxyethylene glycol of-OH and its mixture.
The term lower aliphatic alcohols generally includes: methyl alcohol, ethanol, n-propyl alcohol, Virahol, glycol monomethyl C
1-C
2Alkyl oxide and its mixture.
Also can add various additives.Suitable additive comprises: tensio-active agent, surface-active agents, defoamer, corrosion inhibitor and biocides.
Preferred surface-active agents or tensio-active agent are the nonionic surface active agent that contains the polyalkylene oxide part.By with the ethoxylation of acetylene series dibasic alcohol, for example (Surfynol 465, by Air Products and Chemicals, Inc. for the tetramethyl decynediol of ethoxylation, Allentown, PA 18195 provides) obtain the particularly preferred nonionogenic tenside of a class.
Term " biocides " is used for describing the various antifungal compounds that various fungies grow at long-time residing ink composite that are used for preventing or controlling.Preferred biocides is 1,2-benzisothiazole-3-ketone (Proxel
_GXL, ICI Americas Inc., Wilmington, Delaware 19897).
Corrosion inhibitor is joined in the ink formulations so that suppress or reduce the corrosion of ink-jet printer metal parts, particularly jet pipe/nozzle.A preferred class corrosion inhibitor be 1H-benzotriazole category and 1H-benzotriazole itself be exactly preferred corrosion inhibitor (Cobratec 99, PMCSpecialties, Cincinatti, OH).
The invention provides the aqueous ink prescription that is used for the invisible clear near-infrared fluorescent mark of spray ink Printing, it has overcome the shortcoming of existing printing ink.Printing ink of the present invention mark invisible for printing, that need then detect or discern at this place for example bar code on various porous or half porous substrate (for example paper or paper product) is useful especially.This cannot see mark can be on white or chromatic background.
When it was exposed to ir radiation, printing ink of Xing Chenging and mark had very important photoluminescent property thus.Detect the light of this emission with the near-infrared radiation detector, make the article that the film forming polymer composition of shape is applied on it that invisible " mark " or " mark " be arranged.
According to prior art, it is unexpected that the sulfopolyester/acid amides that contains the near-infrared fluorescent group of copolymerization can be used to prepare the suitable printing ink that is used for spray ink Printing with good stability, and this printing ink can be used for mark or the various substrates of mark to be used for identification/evaluation purpose.This result is unexpected especially because since the maximum absorption wavelength of aggregated dye significantly to moving, so the monomer near-infrared fluorescent group that preparation is advanced in the solvent-based ink absorbs at required wavelength place loss a lot (light) than the low value direction.This aggregated dye has reduced photoluminescent property widely.
Following embodiment further specifies practice of the present invention.The logarithmic viscosity number that provides herein is at 25 ℃, and the solvent that every 100ml is made up of 60 weight part phenol and 40 weight part tetrachloroethane is with the 0.25g polymer determination.Weight-average molecular weight that relates to herein (Mw) and number-average molecular weight (Mn) value are measured by gel permeation chromatography (gpc).
Embodiment 1
Components I-VII is joined 500ml to be equipped with at the bottom of the garden of vacuum outlet, agitator, condensator outlet and nitrogen inlet in the beaker.
I 81.77g (0.421m) m-phthalic acid dimethyl esters
II 24.80g (0.0837m) 5-sodium sulfoisophthalic acid dimethyl esters
III 44.11g (0.416m) Diethylene Glycol
IV 34.07g (0.236m) 1,4 cyclohexane dimethanol
V 0.75g (0.0088m) anhydrous sodium acetate
The Ti catalyzer of VI 100ppm is different third titanium oxide
VII 0.28g (3.6 * 10
-4M) Infrared fluorescence compound-NcSi (OH)
2[people such as Wheller, J.A.C.
S．Vol．106，No．24，1984，pp?7404-7410](Nc=naphthalocyanine)。
This beaker and thing wherein be immersed in 200 ℃ the Belmont metal bath and stir and on reaction mixture, purged nitrogen in 1.0 hours simultaneously.With 5 minutes with this bath temperature be elevated to 220 ℃ and remain on 220 ℃ 2.0 hours.In order to finish polycondensation, reaction mixture temperature is elevated to 250 ℃, use vacuum so that pressure is reduced to 0.5mmHg, and continue heating 20 minutes at 250 ℃.Use the Wiley shredder to grind so that the logarithmic viscosity number of the resulting polymers by the 2mm sieve (I. V .) be 0.275, weight-average molecular weight (Mw) is 14867, number-average molecular weight (Mn) is 3848, polymolecularity (Mw/Mn) is 3.86, and glass transition temp (Tg) is 48.4 ℃ and contains 0.2% (weight) the near-infrared fluorescent group (NIRF) (2000ppm) that has an appointment.
Embodiment 2
Water that will part (100g) embodiment 1 stirs dispersible containing in the distilled water (250ml) that sulfopolyester joins 95 ℃ in batches simultaneously.Stir this mixture up to the dispersion of finishing this polymkeric substance, then cooling.Containing the dispersible gross weight that contains this aqueous dispersion of sulfopolyester of 29% (weight) this water of having an appointment is 343g, and Fan Ying NIRF is about 2000ppm therein.
Embodiment 3
Near-infrared fluorescent is rolled into a ball PcAl-OC
6H
3-3,5-two CO
2CH
3(0.7g, 9.36 * 10
-4M) (embodiment 29 of US5397819) thus mix and reaction preparation and identical condensation polymer described in the embodiment 1 with the component I of top embodiment 1-IV.The dispersible polyester that contains sulfo group of Zhi Bei water contains (5000ppm) the copolymerization NIRF compound therein of 0.5% (weight) of having an appointment like this, and the sieve in the Wiley grinding machine for grinding so that by 2mm.The I of this polymkeric substance. V. be 0.293, Tg is 52.6 ℃, and Mw is 16244, Mn be 4510 and polymolecularity be 3.60.
Embodiment 4
Polymkeric substance that will part (100g) embodiment 3 joins in 95-100 ℃ the distilled water (250ml) in batches and stirs simultaneously.Stir this mixture up to finishing dispersion, then cooling.Containing the dispersible gross weight that contains this aqueous dispersion of sulfopolyester of 30% (weight) water of having an appointment is 337.5g, and Fan Ying NIRF is about 5000ppm therein.
Embodiment 5
Use 0.14g (1.8 * 10
-4M) the outer fluorescent chemicals-NcSi (OH) of equal red
2Thereby-repeat embodiment 1 to obtain containing (1000ppm) polymkeric substance of near-infrared fluorescent group of 0.1% (weight) of having an appointment.The I of this polymkeric substance. V. be 0.268, Tg is 49.2 ℃, and Mw is 15092, Mn be 6582 and polymolecularity be 2.29.
Embodiment 6
Polymkeric substance that will part (110g) embodiment 5 joins in 95-100 ℃ the distilled water (275ml) in batches and stirs simultaneously.Stir this mixture up to finishing dispersion, then cooling.Containing the dispersible gross weight that contains this aqueous dispersion of sulfopolyester of 30% (weight) water of having an appointment is 365.5g, and the NIRF that this polyester reacts therein is about 1000ppm.
Embodiment 7
Use 0.7g (9.0 * 10
-4M) the outer fluorescent chemicals-NcSi (OH) of equal red
2Thereby-repeat embodiment 1 to obtain containing (5000ppm) polymkeric substance of near-infrared fluorescent group of 0.5% (weight) of having an appointment.The I of this polymkeric substance. V. be 0.288, Tg is 51.0 ℃, and Mw is 16372, Mn be 4643 and polymolecularity be 3.52.
Embodiment 8
Polymkeric substance that will part (100g) embodiment 7 joins in 90-95 ℃ the distilled water (250ml) in batches and stirs simultaneously.Stir this mixture up to finishing dispersion, then cooling.Containing the dispersible gross weight that contains this aqueous dispersion of sulfopolyester of 30% (weight) water of having an appointment is 334.6g, and the NIRF that this polyester reacts therein is about 5000ppm.
Embodiment 9
Components I-VII is joined 500ml to be equipped with in the round bottom beaker of vacuum outlet, agitator, condensator outlet and nitrogen inlet.
I 116.78g (0.602m) m-phthalic acid dimethyl esters
II 35.40g (0.120m) 5-sodium sulfoisophthalic acid dimethyl esters
III 63.07g (0.595m) Diethylene Glycol
IV 48.68g (0.338m) 1,4 cyclohexane dimethanol
V 0.98g (0.120m) anhydrous sodium acetate
The Ti catalyzer of VI 75ppm is different third titanium oxide
VII 0.40g (5.3 * 10
-4M) Infrared fluorescence compound-PcAl-OC
6H
3-3,5-two-CO
2CH
3(Pc=phthalocyanine)
[compound of US5397819 embodiment 29]
This beaker and thing wherein be immersed in 200 ℃ the Belmont metal bath and stir and on reaction mixture, purged nitrogen in 1.0 hours simultaneously.With 5 minutes with this bath temperature be elevated to 220 ℃ and remain on 220 ℃ 2.0 hours.Finish polycondensation by reaction mixture temperature being elevated to about 250 ℃, use vacuum and pressure is reduced to 0.1mmHg and heated 15 minutes.Use the Wiley shredder to grind so that the I of the resulting polymers by the 2mm sieve. V. be 0.271, weight-average molecular weight (Mw) is 14458, number-average molecular weight (Mn) is 7162, polymolecularity (Mw/Mn) is 2.0, and glass transition temp (Tg) is 48.8 ℃ and contains 0.2% (weight) the polymer fluorescent group (2000ppm) that has an appointment.
Embodiment 10
The water dispersible polymers that contains sulfo group that will part (150g) embodiment 9 joins in 95-100 ℃ the distilled water (375ml) and stirs up to the dispersion of finishing this polymkeric substance cooling then simultaneously.Containing the dispersible gross weight that contains this aqueous dispersion of sulfopolyester of 29% (weight) water of having an appointment is 514.7g, and Fan Ying NIRF is about 2000ppm therein.
Embodiment 11
With 2 (3), 11 (12), 20 (21), 29 (30)-four-tertiary butyl NcAlCl (5.0g, 0.005m) (product of US5397819 embodiment 34), 5-hydroxyisophthalic acid dimethyl ester (1.05g, 0.005m) mixture heating up of (Aldrich) and pyridine (200ml) and under refluxing, stirring 55 hours altogether.After the cooling this reaction mixture is immersed in the water (500ml).Collect i.e. 2 (3), 11 (12), 20 (21), 29 (30)-four-tertiary butyl NcAl-OC of product by filtering
6H
3-3,5-two CO
2CH
3, wash with water and dry air (yield-4.9g).
Embodiment 12
With the component I-VI of embodiment 9 and near-infrared fluorescent group (0.4g, 3.4 * 10 of top embodiment 11
-4M) mix and carry out 9 described polyreactions as embodiment.The dispersible sulfopolyester of Zhi Bei water contains the NIRF compound of the 2000ppm that has an appointment, its I like this. V. and be 0.27, Tg is 49.9 ℃, and weight-average molecular weight (Mw) is 13986, and number-average molecular weight (Mn) is 4088, and polymolecularity is 3.42.
Embodiment 13
Polymkeric substance that will part (150g) embodiment 12 joins in 95-100 ℃ the distilled water (375ml) in batches and stirs simultaneously.Continue to stir up to the dispersion of finishing this polymkeric substance, then with this mixture cooling.The gross weight that contains this aqueous dispersion of 29.6% (weight) polymkeric substance of having an appointment is 507.5g.
Embodiment 14
With components I-VI and the near-infrared fluorescent group 2 (3), 9 (10), 16 (17) of embodiment 9,23 (24)-four phenoxy groups-Pc-Si (OC
6H
4-4-CO
2CH
3)
2(0.4g, 3.3 * 10
-4M) (product of US5397819 embodiment 24) mixes and carries out the 9 described polyreactions as embodiment.The dispersible sulfopolyester of Zhi Bei water contains 0.2% (weight) the NIRF compound (2000ppm) of having an appointment like this, its I. V. be 0.24, Tg is 49.5 ℃, and weight-average molecular weight (Mw) is 13591, number-average molecular weight (Mn) is 4391, and polymolecularity is 3.1.
Embodiment 15
Polymkeric substance that will part (150g) embodiment 14 joins in 95-100 ℃ the distilled water (375ml) in batches and stirs simultaneously.Continue to stir up to the dispersion of finishing this polymkeric substance, then with this mixture cooling.The gross weight that contains this aqueous dispersions of 29.7% (weight) polymkeric substance of having an appointment is 505g.
Embodiment 16
(it contains the NcSi (OH) of near-infrared fluorescent group that the 5000ppm that has an appointment reacts therein to contain the dispersible polyester of water of sulfo group as above-mentioned embodiment 7 preparation 150g
2), and it is joined in batches (375ml) stirs simultaneously in 95-100 ℃ the distilled water.Stir this mixture up to the dispersion of finishing this polymkeric substance, allow its cooling then.The gross weight that contains this aqueous dispersion of 30% (weight) polymkeric substance of having an appointment is 512.8g.
Embodiment 17
Preparation is used for the NIRF printing ink of the 780nm of continous inkjet printing
By using moderate shear in the Cowels dissolver, to mix 25 minutes, components I-VII is mixed so that preparation contains the NIRF printing ink that about 120ppm near-infrared fluorescent is rolled into a ball.
The component number
Divide
The aqueous solution that contains 29.0% (weight) sulfopolyester of 8.00 parts of embodiment 16 of I, this polyester contain the NcSi (OH) of 5000ppm
2Residue
6.80 parts of propylene glycol of II
84.30 parts of deionized waters of III
0.50 part of Surfynol 465 tensio-active agent of IV (the tetramethyl decynediol tensio-active agent of ethoxylation)
(Air?Products?and?Chemicals，Inc．)
0.25 part of Surfynol of V, 104 PG defoamers (mixture of tetramethyl decynediol and propylene glycol) (Air
Products?and?Chemicals，Inc．)
0.10 part of Proxel of VI
_GXL (30% (weight) aqueous solution) biocides (ICI Americas, Inc.)
[50% (weight) 1H-benzotriazole (PMC Specialties) is the third two for 0.05 part of corrosion inhibitor of VII
Solution in the alcohol] 100.00 parts
Versapor 3000 (3 μ), the Versapor 1200 (1.2 μ) that obtains by deep filter (ultra-thin glass fabric filter), from Gelman Sciences and the composition of Versapor 800 (0.8 μ) the above-mentioned preparation of vacuum filtration continuously.The viscosity of Zhi Bei printing ink is 1.0 centipoises like this, and pH is 6.72, and specific conductivity is 437 micro-ohms, and median size is 0.018 micron (μ), and surface tension is 30.53dynes/cm.Use Scitex 5100 ink-jet printers (ScitexDigital Printing, Inc., Dayton, OH 45420-4099) to print invisible 39 yards bar code on the paper for no reason at a high speed.
Embodiment 18
Low viscosity ink
Be to use 6.00 parts of component II as 17 of embodiment, 84.35 part component III, 1.00 parts of component IV and 0.50 part of component V, the preparation surface tension is 27.88dynes/cm, specific conductivity is the printing ink of 517 micro-ohms, uses this printing ink successfully to print invisible bar code as embodiment 17.
Embodiment 19
Preparation is used for the NIRF printing ink of the 680nm of continous inkjet printing
As described in embodiment 17, filter then so that preparation contains the NIRF printing ink that about 120ppm near-infrared fluorescent is rolled into a ball by using moderate shear in Cowels dissolver/mixing machine, to mix components I-VII to be mixed in 22 minutes.
The component umber
The aqueous solution that contains 29.0% (weight) sulfosalicylic polymer of 20.0 parts of embodiment 10 of I, this polymkeric substance contains
The PcAlOC of 2000ppm
6H
3-3,5-two CO
2CH
3Residue
6.00 parts of propylene glycol of II
73.10 parts of deionized waters of III
0.50 part of Surfynol 465 of IV
0.25 part of Surfynol 104 PG of V
0.10 part of Proxel of VI
_GXL (30% (weight) aqueous solution)
100.00 parts of 0.05 part of corrosion inhibitors of VII [solution of 50% (weight) 1H-benzotriazole in propylene glycol]
The viscosity of Zhi Bei printing ink is 1.01cps like this, surface tension is 32.97dynes/cm, specific conductivity is 513 micro-ohms, median size is 0.015 μ, pH is 6.90 and uses ACS Sensor II spectrophotometer (Applied Color Sysytem) mensuration visible light/near infrared light absorption spectrum to be maximum absorption (λ max) at the 679nm place.As described in embodiment 17, successfully printing bar code on the paper for no reason.
Embodiment 20
19 of similar embodiment are to use 30% (weight) sulfopolyester that contains of 8.00 parts of embodiment 4, and (it contains the PcAlOC of 5000ppm
6H
3-3,5-two CO
2CH
3) as the component I, it is the printing ink of 502 micro-ohms for-27.68dynes/cm and specific conductivity that 84.35 parts of component III, 1.00 parts of component IV and 0.50 part of component V prepare surface tension.As embodiment 17, successfully printing bar code on the paper for no reason.
Embodiment 21
As described in the embodiment 19 be to use 20.00 parts of embodiment 13 contain 29.6% (weight) sulfopolyester (its contain 2000ppm the NIRF compound [2 (3), 11 (12), 20 (21), 29 (30)-four-tertiary butyls-NcAl-OC
6H
3-3,5-two CO
2CH
3]) aqueous solution prepare printing ink as components I.
Embodiment 22
As described in the embodiment 19 be to use 20.00 parts of embodiment 15 contain 29.7% (weight) sulfopolyester (its contain 2000ppm the NIRF compound [2 (3), 9 (10), 16 (17), 23 (24)-four phenoxy groups-PcSi (OC
6H
4-4-CO
2CH
3)
2]) aqueous solution prepare printing ink as components I.
Embodiment 23
Preparation is used for the NIRF printing ink of the 780nm of single nozzle continous inkjet printing
Components I-VI mixed in 25 minutes by using moderate shear in Cowels dissolver/mixing machine, to mix, contain the NIRF printing ink that about 120ppm near-infrared fluorescent is rolled into a ball by a series of deep filters (ultra-thin glass fabric filter), the Versapor 3000 (3 μ), Versapor 1200 (1.2 μ) vacuum filtration that obtain from Gelman Sciences so that prepare then.
The component umber
The aqueous solution that contains 29.0% (weight) sulfopolyester of 8.0 parts of embodiment 16 of I, this polyester contains 5000ppm
NcSi (OH)
2Residue
41.00 parts of propylene glycol of II
41.90 parts of deionized waters of III
9.00 parts of n-propyl alcohols of IV
0.05 part of Proxel of V
_GXL (30% (weight) aqueous solution) biocides
100.00 parts of 0.05 part of corrosion inhibitors of VI (50% the solution of 1H-benzotriazole in propylene glycol)
The viscosity of Zhi Bei printing ink is 5.0cps like this, surface tension is 34.5dynes/cm, and specific conductivity is 123 micro-ohms and uses Domino Codebox 2 printers (Domino Amjet, Inc., Gurnee, IL 60031) successfully make it print invisible mark on paper for no reason.
Embodiment 24
The bubbling jetted ink (670nm) that preparation drips as required
By the Cowels dissolver/mixing machine that uses moderate shear components I-VI mixing was obtained containing the NIRF printing ink that about 120ppm near-infrared fluorescent is rolled into a ball in 25 minutes.
The component umber
The aqueous solution that contains 30.0% (weight) sulfopolyester of 8.0 parts of embodiment 4 of I, this polyester contains 5000ppm
PcAl-OC
6H
3-3,5-two CO
2CH
3Residue
45.00 parts of propylene glycol of II
45.85 parts of deionized waters of III
1.00 parts of Surfynol 465 of IV
0.10 part of Proxel of V
_GXL (30% (weight) aqueous solution)
100.00 parts of 0.05 part of corrosion inhibitors of VI (50% the solution of 1H-benzotriazole in propylene glycol)
The viscosity of Zhi Bei printing ink is that 5.0cps and use drip bubbling ink-jet printer Kodak Diconix 180Si Printer (Eastman Kokak Company as required like this, Rochester, New York 4650) thus successfully making it print bar code on paper for no reason obtains invisible mark.
Embodiment 25
The bubbling jetted ink (780nm) that preparation drips as required
As described in the embodiment 24 just components I be that (it contains the NcSi (OH) of 5000ppm for 30.0% (weight) sulfopolyester that contains of 8.00 parts of embodiment 8
2) aqueous solution, preparation printing ink also is used to print invisible bar code.The viscosity of this printing ink is 4.5cps.
Embodiment 26
The piezoelectricity pulse jetted ink that preparation drips as required
Contain the NIRF printing ink that about 180ppm near-infrared fluorescent is rolled into a ball by under moderate shear, mixing by gravity filtration thereby components I-V to be mixed to prepare then in 10 minutes.
The component umber
The aqueous solution that contains 29.0% (weight) sulfopolyester of 30.0 parts of embodiment 2 of I, this polyester contains 2000ppm
NcSi (OH)
2Residue
65.00 parts of propylene glycol of II
4.85 parts of n-propyl alcohols of III
0.10 part of Proxel of IV
_GXL (30% (weight) aqueous solution)
100.00 parts of 0.05 part of corrosion inhibitors of V (50% the solution of 1H-benzotriazole in propylene glycol)
The viscosity of Zhi Bei printing ink is 19.5cps like this, and surface tension is 36.63dynes/cm and is useful to using the piezoelectricity pulse inkjet printing methods that drips as required to print invisible mark.
Embodiment 27
The piezoelectricity pulse jetted ink that preparation drips as required
Contain the NIRF printing ink that about 180ppm near-infrared fluorescent is rolled into a ball by under moderate shear, mixing by gravity filtration thereby component I-VII to be mixed to prepare then in 10 minutes.
The component umber
The aqueous solution that contains 29.0% (weight) sulfopolyester of 30.0 parts of embodiment 2 of I, this polyester contains 2000ppm
NcSi (OH)
2Residue
50.00 parts of propylene glycol of II
10.00 parts of glycerine of III
4.85 parts of deionized waters of IV
5.00 parts of n-propyl alcohols of V
0.10 part of Proxel of VI
_GXL (30% (weight) aqueous solution)
100.00 parts of 0.05 part of corrosion inhibitors of VII (50% the solution of 1H-benzotriazole in propylene glycol)
The viscosity of Zhi Bei printing ink is 18.0cps like this, and surface tension is 37.04dynes/cm and is useful to using the piezoelectricity pulse inkjet printing methods that drips as required to print invisible mark.
The viscosity of reporting among the top embodiment is to use Shell Cup #2 Viscometer (Newton, MA 02158 for Morcross Corporation, 255 Newtonville Ave.) to measure with the cp of centipoise unit.Surface tension is to use Surface Force AnalyzerSFA-211 (16207 South Carmenita Rd., Cerritus, CA 90701 for Cahn Instrument, Inc.) to measure with Dynes/cm.Median size is to use Microtrac-Ultrafine Particle Analyzer Model 9230-1-00-1 (Leadsand Northrup Co., Sunneytown Pike, North Wales, PA 19454) measure with micron (μ), specific conductivity is to use YSI Model 32 Conductance Meter (YellowSprings Instrument Co., Inc., Scientific Division, YellowSprings, OH 45387) measure with micro-ohm.
Embodiment 28-9 and comparative example
Method with embodiment 24 prepares the ink composite that 2%, 10% and 20% (weight) contains the NIRF polymkeric substance that has of listing in the following table 2.
Table 2
| Component | The % polymkeric substance | |||
| Embodiment # | ????28 | ????29 | Comparative example 1 | Comparative example 2 |
| Propylene glycol | ????42.60 | ????32.50 | ????15.00 | ????1.50 |
| ????NIRF | ????6.70 | ????33.40 | ????50.00 | ????66.70 |
| ????Surfynol?465 | ????1.00 | ????1.00 | ????1.00 | ????1.00 |
| DI water | ????49.55 | ????32.95 | ????33.85 | ????30.65 |
| Corrosion inhibitor (50%) | ????0.05 | ????0.05 | ????0.05 | ????0.05 |
| ????Proxel?G)X1(30％) | ????0.10 | ????0.10 | ????0.1 | ????0.10 |
| ????Total | ????100.00 | ????100.00 | ????100.00 | ????100.00 |
| Viscosity (#2 shell cup in seconds) | ????14.5 | ????15.5 | ????15.0 | ????15.0 |
| Viscosity (cps) | ????4.7 | ????5.5 | ????5.0 | ????5.0 |
Fill 8 Kadak Diconix 180 Si printheads (filling 2 printheads) with the printing ink of listing in the table 1 with each printing ink.Each printhead is put in the Kadak Diconix 180 Si printers with the timed interval that following table 3 provides.Under 68 and 65% relative humidity, print.When not in use, under 68 and 65% relative humidity, store this printhead.If this printhead can not be printed, so by pressing the printing ink bladder to pour into this printhead by spout up to printing ink.Wipe clean printhead and try again with nonlinting cloth then and start.The results are shown in the following table 3.
Table 3
| Embodiment # | Polymkeric substance in the % printing ink | 1 hour | 3 days | 10 days | 20 days | 34 days |
| ????28 | ????2％ | ????4 | ????4 | ????4 | ????4 | ????4 |
| ????28 | ????2％ | ????4 | ????4 | ????4 | ????4 | ????4 |
| ????29 | ????10％ | ????4 | ????4 | ????4 | ????4 | ????4 |
| ????29 | ????10％ | ????4 | ????4 | ????4 | ????4 | ????4 |
| Comparative example 1 | ????15％ | ????4 | ????2 | ????1 | ????1 | ????1 |
| Comparative example 1 | ????15％ | ????4 | ????2 | ????1 | ????1 | ????1 |
| Comparative example 2 | ????20％ | ????0 | ????0 | ????0 | ????0 | ????0 |
| Comparative example 2 | ????20％ | ????0 | ????0 | ????0 | ????0 | ????0 |
The non-constant of 0-; Adhere to nozzle; Can not spray ink Printing
1-is poor; Adhere to nozzle; Repeatedly (＞3) start and can not print; Can not＞1 printing
2-is medium; Spray ink Printing all after starting 3 times
3-is good; Spray ink Printing all after starting 1-2 time
4-is fabulous; Need not to start
Having the printing ink that is similar to the US5336714 composition all can not print at any time at interval.The printing ink nozzle is adhered to and can not be discharged by starting.Yet unexpected is that printing ink of the present invention all demonstrates fabulous printing during whole test.Although printing ink of the present invention contains the NIRF (being in a ratio of 1/100-1/2 with US5336714) of extremely low amount, this printing ink has still formed detectable fluorescent signal.
Claims (16)
1. ink composite comprises:
A.1-10% the dispersible polyester of at least a water of (weight), it comprises:
(ⅰ) monomer residue of at least a dicarboxylic acid;
(ⅱ) in the total amount of all acid, hydroxyl and amino equivalent, 4-25%'s (mole) contains the monomer residue that at least one key is linked at least a double functional group's sulfomonomer of the sulfonation group on the aromatic nucleus, and wherein functional group is hydroxyl, carboxyl, carboxylicesters or amino;
(ⅲ) monomer residue of at least a dibasic alcohol or dibasic alcohol and two amine mixt; Randomly,
(ⅳ) at least a monomer residue that is selected from the difunctional monomer reactant of hydroxycarboxylic acid, aminocarboxylic acid and aminoalkanol;
Condition is: the group that at least 20% key connects this monomeric unit is an ester bond; The dispersible polyester of described water has 0.1ppm-10% (weight) copolymerization heat-staple near infrared fluorescent compound therein;
B.5-75% at least a tackiness agent of (weight);
C.0-15% the rudimentary aliphatic alcohol of at least a no more than 3 carbon atoms of (weight);
D. water and optional one or more additives that are up to 2% (weight);
Wherein the weight percentage of component A-D equals 100%.
2. the composition of claim 1, the dispersible polyester of wherein said water be sulfopolyester and wherein the dibasic alcohol of component (ⅲ) contain in 100% (mole) dibasic alcohol:
(a) the formula H (OCH of at least 15% (mole)
2CH
2)
nThe dibasic alcohol of OH, wherein n is 2-20, or (b) formula H (OCH of 0.1-15% (mole)
2CH
2)
nPoly-(ethylene glycol) of OH, wherein n is 2-500, condition is: the molecular fraction and the n value of above-mentioned poly-(ethylene glycol) are inversely proportional to.
3. the composition of claim 1, it contains:
A. the dispersible polyester of described water;
B.45-75% the described wetting agent of (weight);
C.2-15% the described lower aliphatic alcohols of (weight);
D. water; At least a corrosion inhibitor of 0.01-0.50% (weight); And at least a biocides of 0.01-0.30% (weight).
4. the composition of claim 1, it also contains:
A. the dispersible polyester of described water;
B.20-60% the described wetting agent of (weight);
C.0.50-1.5% at least a tensio-active agent of (weight);
D. water; At least a corrosion inhibitor of 0.01-0.50% (weight); And at least a biocides of 0.01-0.30% (weight).
5. the ink composite of claim 1, it contains:
A. the dispersible polyester of described water;
B.4-8% the described wetting agent of (weight);
C.0.35-0.65% at least a tensio-active agent of (weight);
D. water; At least a defoamer of 0.75-1.25% (weight); At least a corrosion inhibitor of 0.01-0.50% (weight); And at least a biocides of 0.01-0.30% (weight).
6. the ink composite of claim 1, it contains:
A. the dispersible polyester of described water;
B.30-50% at least a described wetting agent of (weight);
C.5-15% at least a described alcohol of (weight);
D. water; At least a corrosion inhibitor of 0.01-0.50% (weight); And at least a biocides of 0.01-0.30% (weight).
7. the ink composite of claim 1, wherein said wetting agent is selected from: ethylene glycol, propylene glycol, butyleneglycol, glycerine, M
nFormula H-(OCH for 200-10000
2-CH
2)
nPoly-(ethylene glycol) of-OH, M
nBe poly-(ethylene glycol) methyl ether of 250-5000, polyvinyl alcohol, polyvinylpyridine, and Polyvinylpyrolidone (PVP) and its mixture.
8. the ink composite of claim 1, wherein said wetting agent is selected from: ethylene glycol, propylene glycol, butyleneglycol, glycerine, wherein n is the formula H-(OCH of 2-6
2-CH
2)
nPoly-(ethylene glycol) and its mixture of-OH.
9. the composition of claim 1, wherein this near infrared fluorescent compound is selected from: phthalocyanine, naphthalene cyanines and squaraines and corresponding to the compound of following formula II, III and IV:
The phthalocyanine and 2 of Pc and Nc expression II a and III a wherein, 3-naphthalene cyanines part,
Respectively, its covalently key link on hydrogen or various metal, halo metal, organometallic group and the oxidized metal, comprise AlCl, AlBr, AlF, AlOH, AlOR
5, AlSR
5, Fe, Ge (OR
6)
2, GaCl, GaBr, GaF, GaOR
5, GaSR
6, Pb, InCl, Mg, Mn, SiCl
2, SiF
2, SnCl
2, Sn (OR
6)
2, Si (OR
6)
2, Sn (SR
6)
2, Si (SR
6)
2And Zn,
R wherein
5And R
6Be selected from: the group of hydrogen, alkyl, aryl, aroyl, heteroaryl, lower alkane acyl group, trifluoroacetyl group, following formula:
R
7, R
8And R
9Be selected from independently of one another: the phenyl that alkyl, phenyl or low alkyl group, lower alkoxy or halogen replace;
X is selected from: oxygen, sulphur, selenium, tellurium or formula N-R
10Group, R wherein
10Be hydrogen, cycloalkyl, alkyl, acyl group, alkyl sulphonyl or aryl, perhaps R
10Form aliphatics or aromatic ring with the nitrogen-atoms that is connected them together with R;
Y is selected from: alkyl, aryl, halogen or hydrogen;
R is selected from: unsubstituted or the alkyl, alkenyl, alkynyl group, the C that replace
3-C
8Cycloalkyl aryl, heteroaryl, alkylidene group-
Or alkylidene group
Or
-(X-R)
mBe alkyl sulfonyl-amino, arlysulfonylamino or the group that is selected from following formula :-X (C
2H
4O)
zR
1,
R wherein
1Be hydrogen or definition R as above; Z is the integer of 1-4; Or 2-(X-R)
mCan form the divalent substituent of following formula together:
X wherein
1Be selected from independently of one another :-O-,-S-or-N-R
10And A is selected from: ethylidene, propylidene, trimethylene and use C
1-C
4Alkyl, C
1-C
4The above group of alkoxyl group, aryl and cycloalkyl substituted, 1,2-phenylene and contain 1-3 and be selected from C
1-C
4Alkyl, C
1-C
4Alkoxy or halogen is substituent 1, the 2-phenylene;
R
1And R
2Be selected from independently of one another: hydrogen, low alkyl group, lower alkoxy, halogen, aryloxy, lower alkylthio, arylthio, low alkyl group alkylsulfonyl, aryl sulfonyl, low alkyl group sulfuryl amino, arlysulfonylamino, naphthene sulfamide base amino, carboxyl, the unsubstituted and formamyl that replaces and sulfamyl, elementary alkoxy carbonyl, hydroxyl, lower alkanoyloxy,
R
3And R
4Be selected from independently of one another: hydrogen, low alkyl group, alkenyl or aryl; N is the integer of 0-12; n
1Be the integer of 0-24, m is the integer of 4-16; m
1Be the integer of 0-16, condition is: n+m and n
1+ m
1Be respectively 16 and 24.There to be at least one pet reaction group is condition.
10. the composition of claim 9, wherein this near infrared fluorescent compound is the squaraine of formula IV, wherein R
1And R
2Be carboxyl or elementary alkoxy carbonyl independently of one another.
11. the ink composite of claim 9, wherein this near-infrared fluorescent group is selected from: the naphthalene cyanines of the phthalocyanine of formula II, formula III and its mixture.
12. the composition of claim 9, wherein this near infrared fluorescent compound is 2 of a formula III, 3-naphthalene cyanine compound, and wherein Y is a hydrogen, n
1Be 24, m
1Be 0.
13. the composition of claim 11, wherein this near infrared fluorescent compound is 2 of a formula III, 3-naphthalene cyanine compound, and wherein naphthalene cyanines part key is linked SiCl
2, Si (OH)
2, or Si (OR
6)
2On.
14. the composition of claim 11, wherein this near infrared fluorescent compound is the phthalocyanine compound of formula II, and wherein X is an oxygen, and R is an aryl, and Y is a hydrogen, and m is 4, and n is 12; And wherein phthalocyanine part key is linked AlCl, AlOH, AlOCOCF
3, AlOR
5, SiCl
2, Si (OH)
2, or Si (OR
6)
2On.
15. the ink composite of claim 9, wherein said near infrared fluorescent compound covalent linkage are linked and are selected from the following part: hydrogen, AlCl, AlBr, AlF, AlOH, AlOR
5, AlSR
5, Ge (OR
6)
2, GaCl, GaBr, GaF, GaOR
5, GaSr
5, Mg, SiCl
2, SiF
2, SnCl
2, Sn (OR
6)
2, Si (OR
6)
2, Sn (SR
6)
2, Si (SR
6)
2And Zn.
16. the method for mark goods invisibly comprises that the ink composite with claim 1-15 is coated on the described goods.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96199105 CN1205731A (en) | 1995-10-23 | 1996-10-18 | Water based inks containing near infrared fluorophores |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/546,973 | 1995-10-23 | ||
| CN 96199105 CN1205731A (en) | 1995-10-23 | 1996-10-18 | Water based inks containing near infrared fluorophores |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1205731A true CN1205731A (en) | 1999-01-20 |
Family
ID=5129323
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96199105 Pending CN1205731A (en) | 1995-10-23 | 1996-10-18 | Water based inks containing near infrared fluorophores |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1205731A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7144105B2 (en) | 2000-08-08 | 2006-12-05 | Canon Kabushiki Kaisha | Ink, ink-jet recording process, recorded article, recording unit, ink cartridge, ink-jet recording apparatus, fluorescence enhancing method and method of elongating life time of fluorescence |
-
1996
- 1996-10-18 CN CN 96199105 patent/CN1205731A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7144105B2 (en) | 2000-08-08 | 2006-12-05 | Canon Kabushiki Kaisha | Ink, ink-jet recording process, recorded article, recording unit, ink cartridge, ink-jet recording apparatus, fluorescence enhancing method and method of elongating life time of fluorescence |
| CN100393824C (en) * | 2000-08-08 | 2008-06-11 | 佳能株式会社 | Printing ink, ink jet recording process, recording product, recording unit, ink box, ink jet recording device, auxoflorence method and fluorescence prolonging |
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