CN101220221A - Two-part curable ink composition set and ink jet recording method, ink jet recording apparatus, and printed product using the same - Google Patents
Two-part curable ink composition set and ink jet recording method, ink jet recording apparatus, and printed product using the same Download PDFInfo
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- CN101220221A CN101220221A CNA2007101603203A CN200710160320A CN101220221A CN 101220221 A CN101220221 A CN 101220221A CN A2007101603203 A CNA2007101603203 A CN A2007101603203A CN 200710160320 A CN200710160320 A CN 200710160320A CN 101220221 A CN101220221 A CN 101220221A
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Abstract
A two-part curable ink composition set includes an ink composition A which contains at least a photopolymerization initiator and a polymerizable compound and which does not contain a coloring material, and an ink composition B which contains at least a coloring material and a polymerizable compound and which does not contain a photopolymerization initiator, wherein either one or each of the ink composition A and the ink composition B contains a resin emulsion dispersed in the polymerizable compound.
Description
Technical field
The present invention relates to a kind of photo curable ink composition, relate in particular to solidified nature, the two-component-type combined light curing ink composition that stationarity is outstanding, ink jet recording method and the ink-jet recording device and the print of use said composition according to photocuring.
Background technology
Ink jet recording method is the droplet leap that makes ink composition, makes it be attached to recording mediums such as paper again, thus the printing process of printing.This ink jet recording method has the feature that can print high-resolution, high-grade image at high speed.The ink composition that uses in ink jet recording method is main component with aqueous solvent usually, the wetting agents such as glycerine that wherein contain coloring components and be used to prevent stop up.
On the other hand, the paper of the kind that is difficult to permeate at hydrotropisms's ink composition is that coated paper, printed book paper, dry goods or starting material such as impervious metal, plastics are when for example being printed by recording mediums such as the plate of resin manufacture such as phenolic aldehyde, trimeric cyanamide, vinylchlorid, vinylformic acid, polycarbonate, films, require colorant stable and can be fixed on the recording medium for ink composition, contain colorant, light curing agent (free-radical polymerised compound), liquid such as photo-curing ink-jet China ink that form, that stationarity is outstanding such as (optical free radical) polymerization starter etc. so use.
In recent years, the purposes of these photo-curing ink-jets China ink liquid is enlarging, and also begins use in the printing etc. on printing, barcode or date that manufacturing, the printing to printed circuit board, plastic clip, ethenoid resin sheet material, the printing to plastic paste, large-scale billboard, outdoor indoor advertisement at colour filter use.Need further to improve characteristics such as stationarity, weather resistance, wear resistant, solidified nature thereupon.
For characteristics such as the stationarity of improving photo-curing ink-jet China ink liquid, weather resistance, wear resistant, solidified nature, shieldings, proposed in ink composition, to contain the technology of polymer particles.
As one of them, disclose the water system ink composition (for example with reference to patent documentation 1) of the matrix material that contains polymer nano-particle and can be cured according to heat or radioactive rays.Use this China ink liquid, can improve the weather resistance of print.
In addition, the aqueous inkjet ink liquid that has also proposed to contain blended resin particle and water miscible ultraviolet hardening wetting agent in water is with black liquid (for example with reference to patent documentation 2).In this technology, contain in the water system ink composition of high molecular particle, if black liquid passes through nozzle ejection, water section ground or fully from black liquid, evaporate then, therefore residual high molecular particle is accumulated in nozzle, become irreclaimable spray nozzle clogging easily, but, can suppress or eliminate spray nozzle clogging by in this China ink liquid, containing wetting agent.
Also proposed to contain can be when the irradiation radioactive rays aqueous liquid dispersion, liquid medium, the inkjet ink composition (for example with reference to patent documentation 3) of tinting material of the radiation-curing polymer binder of initiation reaction.In this technology, can improve stationarity, and by making polymer binder become the radiation-curing type, can suppress to add the rising of the black fluid viscosity that polymer causes, can not disturb ink-jet to spray.
And then, also propose to contain tinting material, liquid medium, polymer binder and (contained a kind of polymer composition at least, this polymer composition is crosslinked, and is insoluble polymer binder in radiation-curable monomer, radiation-curable prepolymer, radiation-curable oligomer and composition thereof) inkjet ink composition (for example with reference to patent documentation 4).In this technology, can improve stationarity, and polymer binder is crosslinked, and is insoluble, so can suppress to add the rising of the black fluid viscosity that polymer causes.
Patent documentation 1: the spy opens the 2004-250659 communique
Patent documentation 2: the spy opens the 2005-23299 communique
Patent documentation 3: the spy opens the 2005-290362 communique
Patent documentation 4: the spy opens the 2005-314655 communique
Summary of the invention
In the ultraviolet curing ink composition of water system, contain resin particle, and then in black liquid, contain under the situation that polymeric liquid does not take place of water and so on, be difficult on the recording medium that does not have black liquid receiving layer, use, before curing reaction, must need to make the operation of moisture evaporation.Equally, in the ink composition of the organic solvent that contains non-polymerization, also must remove the composition that does not participate in curing reaction.So, preferably in ink composition, do not contain such composition.
In the ink gun of hot mode, must need the composition of the organic solvent etc. of water or non-polymerization because of heat foamable, and by combustiblematerials heating to polymerizable compound and so on, not preferred from the view of security, relative therewith, if use the ink gun of piezoelectric actuator, then do not need heating, so do not need to contain aforesaid solvent, more preferably use the ultraviolet curing ink composition.
Described resin particle can make it disperse in black liquid by mix emulsion or the suspension (following emulsion and the suspension do not distinguished abbreviates " resin emulsion " as) that contains resin particle with other black liquid compositions.Resin emulsion is generally methods such as utilizing suspension polymerization, letex polymerization, micro-emulsion polymerization and makes polymerizable compound micronize in water, makes that it is insoluble in water, micronize and the method made, can be used as the dispersion of water system inevitably and obtains.Used as the starting material of ink composition the time, preferably in ink composition, do not sneak into moisture.In addition, it is also conceivable that and in the organic solvent of non-polymerization, carry out above-mentioned polyreaction, but the one-tenth branch that does not participate in curing reaction is blended in the ink composition.Thereby, as the present invention, most preferredly be to use dispersive resin emulsion in polymerizable compound.Therefore, need replace the dispersion system of the resin emulsion in the organic solvent that is scattered in water system or non-polymerization with polymerizable compound.But polymerization takes place according to heat or light homenergic in common polymerizable compound in the replacement Treatment process, can cause unfavorable conditions such as gelation mostly.
Discoveries such as the inventor, if though use comprises polymerizability functional group but have the solvent exchange that the polymerizable compound (for example ethylene glycol one allyl ether) that the character of radical polymerization does not take place separately carries out dispersion system, then can prevent reactions such as gelation, can not contained the ink composition of the unwanted composition of curing reaction.Then also find,, also can not need the preceding heat treated of curing reaction even on the recording medium that does not have black liquid receiving layer.
The present invention is based on above-mentioned opinion and the invention that proposes, and problem of the present invention is to provide and overcomes the outstanding two-component-type combined light of described technical disadvantages, image solidified nature and stationarity in the past and solidify ink composition, the ink jet recording method that uses this ink composition and ink-jet recording device and print.
As the means that solve described problem, the present invention with the content of record in following (1)～(23) as the specific item of invention.
(1) a kind of two-component-type combined light is solidified ink composition, this ink composition comprises and contains optical free radical polymerization starter and free-radical polymerised compound at least and do not contain the ink composition A of colorant does not contain the optical free radical polymerization starter with containing colorant and free-radical polymerised compound at least ink composition B, it is characterized in that
In any one party or both sides, contain the resin emulsion that is scattered in the free-radical polymerised compound.
(2) solidify ink composition according to above-mentioned (1) described two-component-type combined light, it is characterized in that,
Described ink composition A and B do not contain water.
(3) solidify ink composition according to above-mentioned (1) or (2) described two-component-type combined light, it is characterized in that,
Described resin emulsion is the emulsion with resin of polymerizable group.
(4) solidify ink composition according to any described two-component-type combined light in above-mentioned (1)～(3), it is characterized in that,
As the free-radical polymerised compound of described ink composition A and/or described ink composition B, contain allylic compound and/or N-vinyl compound.
(5) solidify ink composition according to above-mentioned (4) described two-component-type combined light, it is characterized in that,
What contain among described ink composition A and/or the described ink composition B contains allylic compound and/or the N-vinyl compound scope at 20 weight %～80 weight %.
(6) solidify ink composition according to above-mentioned (4) or (5) described two-component-type combined light, it is characterized in that,
It is described that to contain allylic compound be ethylene glycol one allyl ether.
(7) solidify ink composition according to above-mentioned (4) or (5) described two-component-type combined light, it is characterized in that,
Described N-vinyl compound is the N-vinyl formamide.
(8) solidify ink composition according to any described two-component-type combined light in above-mentioned (1)～(7), it is characterized in that,
Free-radical polymerised compound as described ink composition A and/or described ink composition B contains the branched chain type polymkeric substance.
(9) solidify ink composition according to above-mentioned (8) described two-component-type combined light, it is characterized in that,
Described branched chain type polymkeric substance is branch-shape polymer and/or hyperbranched polymer.
(10) solidify ink composition according to above-mentioned (8) or (9) described two-component-type combined light, it is characterized in that,
The concentration of described branched chain type polymkeric substance is 3 weight %～30 weight %.
(11) solidify ink composition according to any described two-component-type combined light in above-mentioned (1)～(10), it is characterized in that,
Described ink composition A and/or described ink composition B contain tensio-active agent.
(12) solidify ink composition according to above-mentioned (11) described two-component-type combined light, it is characterized in that,
As tensio-active agent, use polyether-modified polydimethylsiloxane or polyester modification polydimethylsiloxane.
(13) solidify ink composition according to any described two-component-type combined light in above-mentioned (1)～(12), it is characterized in that,
Described ink composition A and/or described ink composition B contain promoter.
(14) solidify ink composition according to above-mentioned (13) described two-component-type combined light, it is characterized in that,
As described promoter, comprise more than any one of amine compound, thioxanthone, polymerizability particulate.
(15) solidify ink composition according to any described two-component-type combined light in above-mentioned (1)～(14), it is characterized in that,
The described optical free radical polymerization starter that contains among the described ink composition A is any one of alpha-amino group ketone, alpha-alcohol ketone, acylphosphine oxide.
(16) solidify ink composition according to any described two-component-type combined light in above-mentioned (1)～(14), it is characterized in that,
The described optical free radical polymerization starter that contains among the described ink composition A mixes and uses any more than 2 kinds of alpha-amino group ketone, alpha-alcohol ketone, acylphosphine oxide.
(17) solidify ink composition according to any described two-component-type combined light in above-mentioned (1)～(16), it is characterized in that,
Described ink composition A and/or described ink composition B contain the hot radical stopper.
(18) solidify ink composition according to above-mentioned (17) described two-component-type combined light, it is characterized in that,
Described hot radical stopper is the HALS based compound.
(19) solidify ink composition according to any described two-component-type combined light in above-mentioned (1)～(18), it is characterized in that,
The described colorant that contains among the described ink composition B is a pigment.
(20) a kind of ink-jet is solidified ink composition with the two-component-type combined light, it is characterized in that,
Use any described two-component-type combined light curing ink composition in above-mentioned (1)～(19).
(21) a kind of ink jet recording method is characterized in that,
Use above-mentioned (20) described ink-jet to solidify ink composition with the two-component-type combined light.
(22) a kind of ink-jet recording device is characterized in that,
Possess above-mentioned (20) described ink-jet and solidify ink composition with the two-component-type combined light.
(23) a kind of print is characterized in that,
Use above-mentioned (21) described ink jet recording method and/or above-mentioned (22) described ink-jet recording device and form the part of image at least.
Utilize the present invention, can provide the outstanding two-component-type combined light of solidified nature and stationarity to solidify ink composition.Two-component-type combined light of the present invention is solidified ink composition and is applicable to ink jet recording method, can also be used for ink-jet recording device in addition.
Embodiment
Below two-component-type combined light of the present invention solidified ink composition be elaborated.
Two-component-type combined light of the present invention is solidified ink composition and is comprised: contain optical free radical polymerization starter and free-radical polymerised compound at least and do not contain the ink composition A of colorant, contain colorant and free-radical polymerised compound at least and do not contain the ink composition B of optical free radical polymerization starter, wherein, in any one party or both sides, contain the resin emulsion that is scattered in the free-radical polymerised compound.In addition, two-component-type combined light curing ink composition of the present invention does not preferably contain water
For the particulate of dispersion resin in black liquid, it is effective utilizing resin emulsion.Resin emulsion can make polymerizable compound micronize in water by methods such as suspension polymerization, letex polymerization, micro-emulsion polymerizations usually, and make that it is insoluble in water, micronize and making, the dispersion that must can be used as water system obtains.
As the resin particle that the above-mentioned polymerizable compound of polymerization obtains, can enumerate multipolymers such as polystyrene, acrylic acid series, ethene system, epoxy system, polyamide-based, polyester system or styrene-propene acid copolymer.As multipolymer, can enumerate polymerization random copolymers that different monomers forms more than 2 kinds or segmented copolymer.The resin that obtains is not particularly limited, from viewpoints such as the weather resistance of the stationarity of recording medium or print, wear resistant, be identical material preferably with recording medium.
Above-mentioned random copolymers can for example make its polymerization obtain mixing different monomers more than 2 kinds under the state of mix monomer A and monomers B, as-ABBABBBAAABA, be the polymkeric substance that the random arrangement of monomeric unit forms.In addition, above-mentioned segmented copolymer is the polymkeric substance with structure as described below, that is, the oligomer BBBB that oligomer AAA that polymerization single polymerization monomer A obtains and polymerization single polymerization monomer B are obtained polymerization takes place and the structure as-AAABBBBAAABBBB that obtains.
The particulate of above-mentioned resin preferably has polymerizable group on the surface, so resin is preferably the compound that has polymerizable groups such as acryl, methacryloyl, epoxy group(ing), vinyl at the end of molecule or side chain.Thus, can under rayed, carry out polymerization or can combine, can improve weather resistance, wear resistant of print etc. with other compositions in the black liquid with free-radical polymerised compound.
The various resin emulsions of water system of particulate that are dispersed with above-mentioned resin also can use them by commercially available.As mentioned above, preferably in the light solidified ink composition, do not contain water, so in this case, preferably carry out the solvent exchange of dispersion system.
That is, in the present invention, if, then can prevent reactions such as gelation though find that use contains polymerizability functional group and has the solvent exchange that the polymerizable compound (for example ethylene glycol one allyl ether) that polymeric character does not take place separately carries out dispersion system.Solvent exchange can be easily utilizes the separation method of boiling-point difference to implement by the method for using commercially available rotatory evaporator, wet distillation, underpressure distillation etc.By resin emulsion and other black liquid compositions that mixed solvent displacement obtains, can obtain containing dispersive resin particle and do not contain the ink composition of the unwanted composition of curing reaction.In this ink composition, contain resin particle, but particulate is not dissolved in the solvent, therefore can suppress to rise because of adding the viscosity that resin causes.In addition, do not contain the unwanted composition of curing reaction, so, can save the preceding heat treated of curing reaction even on the recording medium that does not have black liquid receiving layer yet.
And then owing to do not contain the unwanted solvent of curing reaction, therefore light solidified ink composition of the present invention is applicable to that lift-launch do not use the ink gun of hot mode and use the ink-jet recording device of the ink gun of piezoelectric actuator.
The resin emulsion that also can replace water system utilizes non-water system light-cured type resin emulsion.This is known as the solution that adds the polymkeric substance that is dissolved with emulsification in the insoluble non-water system organic solvent of polymkeric substance, carries out blending dispersion, makes the micro polymer granulation, makes the method for non-aqueous resin emulsification thus.As non-water system light-cured type resin emulsion, can enumerate the system Laromer LR of BASF AG 9023, PE46T, LR 8907, UA 19T, UA 9030V, UA 9033V, LR8987, UP 35D etc.Non-water system light-cured type resin emulsion has polymerizable group on the surface of resin particle.If use non-water system light-cured type resin emulsion, then do not need to carry out above-mentioned solvent exchange.
Resin emulsion amount in the ink composition is preferably 1 weight %～20 weight %, and then is preferably 5 weight %～10 weight %.The addition surplus of if tree lipoprotein emulsion then becomes the bad reason of ejection of black drop, if very few, then can not obtain additive effect.In addition, from suppressing the viewpoint of black liquid concentration, compare with the solvent solubility resin, more preferably resin emulsion.
As the optical free radical polymerization starter that uses among the ink composition A of the present invention; be not particularly limited; preferred alpha-amino group ketone, alpha-alcohol ketone, acylphosphine oxide for example can be enumerated alpha-aminoalkyl phenol, alpha-aminoalkyl phenol, an acylphosphine oxide, diacyl phosphine oxide.Alpha-amino group ketone, alpha-alcohol ketone or acylphosphine oxide can use separately or also can mix two or more uses.
In addition, can also use the optical free radical polymerization starter that can obtain with the trade(brand)name of Irgacure 127,184,2959,369,379,907,1700,1800,1850,1870,819,4625, Darocur 1173, TPO (Ciba (CibaSpecialty Chemicals) corporate system).
The addition of optical free radical polymerization starter is preferably 0.1 weight %～15 weight % in ink composition, more preferably 0.5 weight %～10 weight %.Under the very few situation of addition, polymerization velocity is low, so the inhibiting influence of oxygen becomes big, become solidify bad.Under the situation of addition surplus, the molecular weight of cured article is low, can only obtain the low cured article of weather resistance.
As the free-radical polymerised compound that uses among ink composition A and/or the ink composition B, contain allylic compound and/or N-vinyl compound.
Describe containing allylic compound, this compound is to have the allylic compound of polymeric does not take place separately, is to have 2-propenyl structure (CH
2CH=CH
2) the general name of compound.Be also referred to as 2-propenyl or allyl group, in the IUPAC nomenclature, become trivial name.For example, except described ethylene glycol one allyl ether, can also enumerate allyl group glycol (Japanese emulsifying agent system), TriMethylolPropane(TMP) diallyl ether, tetramethylolmethane three allyl ethers, glycerine one allyl ether (above be DAISO Co., Ltd.) or have an allylic polyoxyalkylene (Japanese grease manufacturing) etc. as trade(brand)names such as UNIOX, UNILUB, polyserine (POLYCERIN), UNISAFE.
As containing allylic compound, preferred allyl ether compound.As the allyl ether compound, can enumerate ethylene glycol one allyl ether, TriMethylolPropane(TMP) diallyl ether, TriMethylolPropane(TMP) one allyl ether, glycerine one allyl ether, glycidyl allyl ether, tetramethylolmethane three allyl ethers, preferred especially ethylene glycol one allyl ether, TriMethylolPropane(TMP) diallyl ether, most preferably ethylene glycol one allyl ether.In addition, as the N-vinyl compound, preferred N-vinyl formamide.They can use separately or and use.
Ethylene glycol one allyl ether or N-vinyl compound are the free radical polymerization monomer of simple function, and that undesirable polymeric trend takes place is low because of dark reaction in preservation, are suitable for using.In addition, even particularly allyl ether compounds such as ethylene glycol one allyl ether, TriMethylolPropane(TMP) diallyl ether have the carbon radicals that the decomposition that has the optical free radical polymerization starter produces, also be difficult to independent polymerization, the characteristic that polymer quantizes can not take place.
If the addition that contains allylic compound and/or N-vinyl formamide is less than 20 weight %, then produce the problem of the viscosity of ink composition and dispersion stabilization, package stability etc., become many if surpass 80 weight %, then sometimes as the solidified nature of two-component-type photo curable ink composition, become insufficient by film toughness, so preferred 20 weight %～80 weight %.The more preferably scope of 20 weight %～70 weight %.
In addition, in ink composition A of the present invention and/or ink composition B,, contain the branched chain type polymkeric substance sometimes as free-radical polymerised compound.As the branched chain type polymkeric substance, ground as follows can roughly be divided into 6 structures
I branch-shape polymer (dendrimer)
II linearity-dendritic polymer (linear-dendritic polymer)
The tree-shaped graftomer of III (dendrigraft polymer)
IV hyperbranched polymer (hyperbranched polymer)
V star hyperbranched polymer (star-hyperbranched polymer)
The super graftomer of VI (hypergraft polymer)
Wherein, the branching index of I～III (DB:degree of branching) is 1, compares with the structure with flawless structure, and IV～VI has the random branched structure that can contain defectiveness.Particularly branch-shape polymer is compared with normally used straight catenate polymer, can be at its outermost high-density and concentrated area configuration reactive functional groups, as the possibility height of functional high molecule material.In addition, though hyperbranched polymer does not reach the degree of branch-shape polymer, also can introduce a lot of reactive functional groups at its outermost, solidified nature is outstanding.
These branched chain type polymkeric substance are different with in the past straight chain shape polymer or branched polymer, three-dimensional ground repeat branch structure, and highly branched.So, compare with the straight chain shape polymer of same molecular amount, can suppress viscosity lower.
In the present invention in the synthesis method of operable branch-shape polymer, can enumerate outer synthetic branch (Divergent) method of mind-set therefrom and convergence (Convergent) method of carrying out etc. from export-oriented center.
Operable in the present invention branch-shape polymer or hyperbranched polymer at room temperature are solid, and number-average molecular weight is preferably in 1000～100000 scope, especially preferably use the polymkeric substance of number-average molecular weight in 2000～50000 scope.Molecular weight is lower than under the situation of above-mentioned scope, and the photographic fixing image fogs easily, and in addition, molecular weight is higher than under the situation of above-mentioned scope, even reduce addition, it is too high that black fluid viscosity also can become, and is from ejection characteristic this point, impracticable.
In addition, operable in the present invention branch-shape polymer and/or hyperbranched polymer preferably have the branch-shape polymer and/or the hyperbranched polymer of the functional group that can carry out radical polymerization at outermost.By the structure of outermost for carrying out radical polymerization, polyreaction is promptly carried out.
As the example of polymkeric substance, can enumerate United States Patent (USP) the 4th, 507 with branch-shape polymer structure, No. 466, United States Patent (USP) the 4th, 558, No. 120, United States Patent (USP) the 4th, 568, No. 737, United States Patent (USP) the 4th, 587, No. 329, United States Patent (USP) the 4th, 631, amino amides shown in No. 337, the 4th, 694, No. 064 specification sheets of United States Patent (USP) is a branch-shape polymer; United States Patent (USP) the 5th, 041, the phenyl ether shown in No. 516 specification sheetss, Journal ofAmerican Chemistry 112 volumes (nineteen ninety, 7638～7647 pages) etc. is a branch-shape polymer.For amino amides is branch-shape polymer, and Aldrich company sells the branch-shape polymer with terminal amino group and carboxylate methyl ester base with " StarburstTM (PAMAM) ".In addition, also can make this amino amides is terminal amino group and the various acrylic acid derivative and the methacrylic acid derivative reaction of branch-shape polymer, and synthetic amino amides with corresponding end is a branch-shape polymer, thereby uses them.
As utilizable acrylic acid derivative and methacrylic acid derivative; can enumerate the acrylic or methacrylic acid alkyl ester class of methyl, ethyl, normal-butyl, the tertiary butyl, cyclohexyl, palmitoyl, stearyl-etc.; acrylic or methacrylic such as acrylamide, Isopropamide dialkylaminobenzoic acid amides, but be not limited thereto.
In addition, for phenyl ether is branch-shape polymer, for example roll up (nineteen ninety at above-mentioned Journal of AmericanChemistry 112,7638～7647 pages) in to have put down in writing various phenyl ether be branch-shape polymer, for example put down in writing and used 3, the 5-dihydroxy-benzyl alcohol, make itself and 3, the reaction of 5-two phenoxy group cylites, the benzylalcohol in synthetic the 2nd generation uses CBr
4And triphenyl phosphine converts its OH base to Br, similarly makes it with 3 then, the reaction of 5-dihydroxy-benzyl alcohol, synthetic follow-on benzylalcohol below repeats above-mentioned reaction, synthetic need branch-shape polymer.For phenyl ether is branch-shape polymer, can also replace terminal dibenzyl ether combination, replaces terminal with the material with various chemical structures.For example, roll up (nineteen ninety at synthetic above-mentioned Journal of American Chemistry112,7638～7647 pages) in the record branch-shape polymer the time, use various haloalkanes if replace above-mentioned cylite, the phenyl ether that then can obtain having the end structure that contains the alkyl suitable with it is a branch-shape polymer.Other polyamine are that branch-shape polymer can use Macromol.Symp, and the polyamine shown in 77,21 (1994) is the derivative of branch-shape polymer and its terminal group of modification.
As hyperbranched polymer, for example can use hyperbranched poly ethylene glycol etc.Hyperbranched polymer is to use at 1 intramolecularly with a kind of reflecting point more than 2 that is equivalent to branching part and the another kind that is equivalent to the connection portion monomer of a reflecting point only, material (the Macromolecules that obtains by 1 section synthetic subject polymer, 29 volumes (1996), 3831～3838 pages).For example, with a monomeric example, can enumerate 3,5-protocatechuic acid derivative as hyperbranched polymer.Production Example as hyperbranched polymer, can enumerate with oxalic acid two fourth tin with as by 1-bromo-8-(tert-butyl diphenyl siloxy-)-3,6-two _ octane and 3, the 5-methyl dihydroxy benzoate obtain 3, two ((8 '-(the tert-butyl diphenyl siloxyies)-3 ' of 5-, 6 '-two _ octyl group) oxygen) 3 of the hydrolysate of methyl benzoate, two ((the 8 '-hydroxyls-3 ' of 5-, 6 '-two _ octyl group) methyl benzoate oxygen), under nitrogen atmosphere, heat, thereby can synthesize poly-[two (triethylene glycol) benzoic ether] as hyperbranched polymer.
Use 3, under the situation of 5-resorcylic acid,,, can synthesize hyperbranched polymer with various terminal group so this hydroxyl is suitable haloalkane by using relatively because the hyperbranched polymer terminal group becomes hydroxyl.
Have the monodisperse polymer of branch-shape polymer structure or hyperbranched polymer etc. and control its characteristic by the chemical structure of main chain and the chemical structure of its terminal group, and especially because the substituent difference in terminal group or the chemical structure and its characteristic is greatly different.The polymkeric substance that particularly has polymerizable group endways is because its reactivity and gelation effect after the photoresponse is extremely useful.Branch-shape polymer with polymerizable group can obtain by with the compound with polymerizable group the end of the compound that has basic groups such as amino, substituted-amino, hydroxyl endways being carried out chemically modified.
For example, be that branch-shape polymer Michael (Michael) addition contains among the polyfunctional compound that (methyl) acrylate based compound of reactive hydrogen forms to amino, for example the addition vinyl compound that contains isocyanate group synthesizes.In addition, can also be the branch-shape polymer that the branch-shape polymer reaction is had polymerizable group endways by for example making (methyl) vinylformic acid muriate etc. and amino.As the vinyl compound of giving such polymerizable group, can enumerate compound with the ethene unsaturated link(age) that can carry out radical polymerization, as its example, can enumerate, for example unsaturated carboxylic acid such as vinylformic acid, methacrylic acid, methylene-succinic acid, Ba Dousuan, iso-crotonic acid, toxilic acid and their salt etc. have the various compound that can carry out the ethene unsaturated link(age) of radical polymerization described later.
In the present invention, can only be used alone above-mentioned branch-shape polymer and hyperbranched polymer, also can also use with the branch-shape polymer and the hyperbranched polymer of other kinds.
Solidify among the ink composition A and/or ink composition B of ink composition in two-component-type combined light of the present invention, the addition of above-mentioned branched chain type polymkeric substance is preferably the scope about 3 weight %～30 weight %, can keep solidifying as the two-component-type combined light suitability of ink composition.The more preferably scope about 5 weight %～25 weight %.Under the situation of the addition of branched chain type polymkeric substance less than 3 weight %, the solidified nature of solidifying ink composition as the two-component-type combined light is insufficient, uprise if surpass 30 weight %, then produce the problem of the viscosity, dispersion stabilization, package stability etc. of ink composition sometimes.
Solidify among the ink composition A and/or ink composition B of ink composition in two-component-type combined light of the present invention, also can contain other free-radical polymerised compounds.
As other free-radical polymerised compounds, be not particularly limited, for example can enumerate monomer (monomer).
Monomer is meant the unitary molecule of the formation that can become high molecular basic structure.In addition, the monomer that uses among the present invention is also referred to as " photopolymerization monomer ", comprises monofunctional monomer, two functional monomers, polyfunctional monomer, can use arbitrarily.The all preferred PII value (Primary IrritationIndex, a skin irritation rate) of monomer is below 2 arbitrarily.
The PII value that can use in the present invention is that monofunctional monomer, two functional monomers and polyfunctional monomer below 2 is as illustrated in the following table 1.
[table 1]
| Monofunctional monomer | ||
| The material name | Viscosity (mPas) | P.I.I |
| Vinylformic acid (2-methyl-2-ethyl-1,3-two oxa-s penta ring-4-yl) methyl ester (MEDOL-10, Osaka is organic) | 5.1 | 1.3 |
| Vinylformic acid (2-methyl-2-isobutyl--1,3-two oxa-s penta ring-4-yl) methyl ester (MIBDOL-10, Osaka is organic) | 5.3 | 1.0 |
| Vinylformic acid phenoxy ethyl (Viscoat#192, Osaka is organic) | 3.3 | 1.7 |
| Isobornyl acrylate (IBXA, Osaka is organic) | 2.6 | 0.6 |
| Methoxyl group diglycol monotertiary acrylate (Blemmer PME-100, Japanese grease) | 2 | 0.7 |
| Acryloyl morpholine (ACMO, emerging people) | 12 | 0.5 |
| Two functional monomers | ||
| The material name | Viscosity (mPas) | P.I.I |
| Ethylene glycol dimethacrylate (Light-Ester EG, common prosperity society chemistry) | 3 | 0.6 |
| Diethylene glycol dimethacrylate (Light-Ester 2EG, common prosperity society chemistry) | 5 | 0.5 |
| Tripropylene glycol diacrylate (Aronix M-220, East Asia is synthetic) | 12 | 1.6 |
| 1,9-nonanediol diacrylate (Viscoat#260, Osaka is organic) | 21 | 2.0 |
| Polyoxyethylene glycol #400 diacrylate (NK EsterA400, Xin Zhong village chemistry) | 58 | 0.4 |
| Tetraethylene glycol dimethacrylate (NK Ester 4G, Xin Zhong village chemistry) | 14 | 0.5 |
| 1,6-hexanediol dimethacrylate (NK Ester HD-N, Xin Zhong village chemistry) | 6 | 0.5 |
| Neopentylglycol dimethacrylate (NK Ester NPG, Xin Zhong village chemistry) | 7 | 0.0 |
| 2-hydroxyl-1,3-dimethyl allene acyloxy propane (NK Ester 701, Xin Zhong village chemistry) | 37 | 0.6 |
| 1,4-butylene glycol dimethacrylate (BD, Xin Zhong village chemistry) | 7 | 2.0 |
| Polyfunctional monomer | ||
| The material name | Viscosity (mPas) | P.I.I |
| Trimethylolpropane trimethacrylate (NKEsterTMPT, Xin Zhong village chemistry) | 42 | 0.8 |
| TriMethylolPropane(TMP) modification triacrylate (Viscoat#360, Osaka is organic) | 55 | 1.5 |
| TriMethylolPropane(TMP) PO modification triacrylate (New FrontierTMP-3P, the first industrial pharmacy) | 60 | 0.1 |
| Glycerine PO modification triacrylate (Viscoat#GPT, Osaka is organic) | 75 | 0.8 |
Wherein, the viscosity in the described table is the measured value under 25 ℃.
In addition, the free-radical polymerised compound as two-component-type combined light curing ink composition of the present invention except above-mentioned monomer, also can contain oligomer.
In addition, in containing the ink composition A of optical free radical polymerization starter and free-radical polymerised compound, as long as free-radical polymerised compound is the free radical polymerization monomer of simple function, then in preservation, it is also low with the reaction of optical free radical polymerization starter undesirable polymeric possibility to take place.As monofunctional monomer as used herein, preferred N-vinyl formamide or ethylene glycol one allyl ether etc.
Ink composition A of the present invention and/or ink composition B can use tensio-active agent, for example as the silicone-based tensio-active agent, preferred polyester modification silicone or the polyether modified silicone used, preferred especially polyether-modified polydimethylsiloxane or the polyester modification polydimethylsiloxane of using.As concrete example, can enumerate BYK-347, BYK-348, BYK-UV3500,3510,3530,3570 (BYK-Chemie Japan Co., Ltd. system).
Ink composition A and/or ink composition B that two-component-type combined light of the present invention is solidified ink composition also can contain promoter.As promoter, be not particularly limited, preferably contain more than any one of amine compound, thioxanthone, polymerizability particulate, for example can enumerate Darocur EHA, EDB (Ciba (Ciba Specialty Chemicals) corporate system) as Aminobenzoate, thioxanthone, isopropyl thioxanthone, dimethyl thioxanthone, diethyl thioxanthone, import polymerizability particulate of polymerizability functional group etc. on its surface.
In addition, the ink composition A and/or the ink composition B of two-component-type combined light curing ink composition of the present invention preferably contain the hot radical stopper.Like this, can improve the package stability of ink composition.Can use the hot radical stopper that in common Polymerizable composition, cooperates, for example except phenol such as sterically hindered phenolic compound are that oxidation inhibitor, bulky amine are that photostabilizer (HALS), phosphorus are oxidation inhibitor, the quinhydrones monomethyl ether that in (methyl) Acrylic Acid Monomer, uses widely, can enumerate Resorcinol, tert-butyl catechol, pyrogallol etc., preferred sterically hindered phenolic compound or HALS based compound.
As sterically hindered phenolic compound, for example can enumerate Irgastab UV-22 (Ciba (CibaSpecialty Chemicals) corporate system), as HALS is the hot radical stopper, for example can enumerate Irgastab UV-10 (Ciba (Ciba Specialty Chemicals) corporate system).
In addition, solidify in the ink composition, have only ink composition B to contain colorant in two-component-type combined light of the present invention.From the point of the weather resistance of print, the colorant preferred pigments of Shi Yonging in this case.
Pigment as using in the present invention is not particularly limited, and can use mineral dye, pigment dyestuff.
As mineral dye, except titanium oxide and ferric oxide, can also use and utilize contact process, High Temperature Furnaces Heating Apparatus to make the carbon black that known method such as carbon black method, pyrolysis method are made.In addition, as pigment dyestuff, can use azo pigment (comprising dissolubility azo pigment, insoluble azo colour, condensed azo-pigment, chelating azo pigment etc.), encircle pigment (for example phthalocyanine pigment, the rare pigment of purple perilla, purple cyclic ketones pigment, anthraquinone pigment, quinacridone pigment, two _ piperazine pigment, thioindigo color, isoindolinone pigment, quinophthalone pigment etc.), chelating dyes (for example alkaline chelating dyes, acid chelating dyes etc.), nitropigments, nitroso pigments, Ben An more etc..
In the concrete example of pigment, can enumerate as carbon black, C.I. Yan Liao 7, No.2300, the No.900 of Mitsubishi Chemical Ind's system, MCF88, No.33, No.40, No.45, No.52, MA7, MA 8, MA 100, No.2200 B etc.; The Raven 5750 of Columbia Chemical corporate system, Raven 5250, Raven 5000, Raven 3500, Raven 1255, Raven 700 etc.; The Regal 400R of Cabot corporate system, Regal 330R, Regal 660R, Mogul L, Mogul 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400 etc.; Color Black FW1, the ColorBlack FW2 of Degussa corporate system, Color Black FW2V, Color Black FW18, Color Black FW200, ColorBlack S150, ColorBlack S160, ColorBlack S170, Printex 35, PrintexU, Printex V, Printex 140U, Special Black 6, Special Black 5, Special Black4A, Special Black 4 etc.
As the pigment that is used for yellow black liquid, can enumerate C.I. Pigment Yellow 73 1,2,3,12,13,14,16,17,73,74,75,83,93,95,97,98,109,110,114,120,128,129,138,139,150,151,154,155,180,185,213 etc.
In addition,, can enumerate C.I. Pigment red 5,7,12,48 (Ca), 48 (Mn), 57 (Ca), 57:1,112,122,123,168,184,202,209, C.I. pigment violet 19 etc. as the pigment that is used for magenta ink liquid.
In addition,, can enumerate C.I. pigment blue 1,2,3,1 5:3,15:4,60,16,22 as the pigment that is used for cyan ink liquid.
In addition, as the pigment that uses in the white ink liquid, can enumerate titanium dioxide, lime carbonate, calcium sulfate, zinc oxide, barium sulfate, barium carbonate, silica, aluminum oxide, kaolin, clay, talcum, carclazyte, aluminium hydroxide, magnesiumcarbonate, white hollow resin emulsion etc., be preferably one or more the mixture of from the group of its formation, selecting.
As operable pigment in the metallic ink liquid, be not particularly limited, for example can enumerate to be the border, peel off and pulverize the pigment that forms from described flat substrates by stack gradually the described metal of peeling off the compoundization substance that the structure with resin layer and metal or metal compound layer constitutes or metal compound layer and described interface of peeling off at the flat substrates face with resin layer.
Has functions such as possessing metalluster as long as be used for making the metal of compoundization pigment substance of this tinsel or metal or the metallic compound that metal compound layer uses, be not particularly limited, aluminium, silver, gold, nickel, chromium, tin, zinc, indium, titanium, copper etc. be can use, their elemental metals, their alloy at least a preferably used.In addition, pigment of all kinds is in order to regulate its tone, and use also can be mixed with each other.For example, for Hong De tone become indigo plant, also can Hun close Yan Liao 7 and pigment Blue 15: 3.In addition, also can add white dyes.
If utilize optimal way of the present invention, the median size of inorganic pigment dyestuff is preferably the scope of 10nm～200nm, more preferably about 50nm～150nm.As metallic ink liquid, preferred mean thickness is more than the 30nm, below the 100nm, and 50% volume average particle size is more than the 1.0 μ m, below the 4.0 μ m, and the maximum particle diameter in the size-grade distribution is the following tinsels of 12 μ m.
The addition of the colorant among the ink composition B is preferably the scope about 0.1 quality %～25 quality %, more preferably the scope about 0.5 quality %～15 quality %.
If utilize optimal way of the present invention, these pigment can be used as and utilize dispersion agent or tensio-active agent to make its dispersible pigment dispersion that disperses to obtain in aqueous medium become ink composition B.As preferred dispersing agent, can use for example macromolecule dispersing agent of dispersion agent habitual when the pigment preparation dispersion liquid.
In addition, ink composition B contains under the situation of colorant, and the ink composition that contains this colorant also can every kind of color have multiple colorant.For example, except Huang, magenta, Qing, basic 4 looks, in every kind of color, add under the situation of isonomic dark color or light color, except magenta, light red, the scarlet of light color can also be enumerated, except blue-greenish colour, pale bluish green, mazarine, the purple of light color can also be enumerated.In addition, can also enumerate the green, orange of middle shade.Except Achromatic color De , can also enumerate light color grey, Qian look, dark matte black (matte biack), as Achromatic color white, can also enumerate cream color, ivory white except equally, and then also have silver color as metallic color, gold, coppery, chromium silver color etc.
In addition, as required, also can add levelling property additive, matting agent, the polyester based resin that is used to regulate the film rerum natura, polyurethane series resin, vinylite, acrylic resin, rubber is that resin, polyacrylic acid polyvalent alcohol are resin, polyoxyalkylene polyalkylene polyimide resin, wax class.In addition, in ink composition A of the present invention and/or ink composition B, can also add wetting agent as operable public other compositions in the two-component-type photo curable ink, penetrating solvent, pH regulator agent, sanitas, fungicide etc.
Two-component-type combined light of the present invention is solidified ink composition after mixed ink fluid composition A and ink composition B, is cured reaction by carrying out rayed.Mixing so long as get final product before curing reaction, can be any one party after printing before printing.That is, this mixing and printing can make ink composition A and ink composition B adhere to for the same position at recording medium mode in addition, also can and make it be attached to mode on the recording medium for mixed ink fluid composition A and ink composition B.
Use the ink jet recording method that two-component-type combined light of the present invention is solidified ink composition preferably on recording medium, to spray ink composition, irradiation ultraviolet radiation then.
Radiation source is not particularly limited, and radiation source is preferably the light of the wavelength that 350nm is above, 450nm is following.The ultraviolet irradiation amount is 10mJ/cm
2More than, 20,000mJ/cm
2Below, preferably at 50mJ/cm
2More than, 15,000mJ/cm
2Following scope is carried out.If be the ultraviolet irradiation amount in the scope of this degree, just can be cured reaction fully.
Uviolizing can be enumerated lamps such as metal halide lamp, xenon lamp, carbon arc lamp, chemical lamp, Cooper-Hewitt lamp, high pressure mercury vapour lamp.For example can use the commercially available lamp such as H lamp, D lamp, V lamp of Fusion System corporate system to carry out.In addition, can also utilize the luminescence-utraviolet semiconductor element of ultraviolet LED (ultraviolet LED) or luminescence-utraviolet semiconductor laser etc., carry out uviolizing.
Utilization possesses the ink-jet recording device that two-component-type combined light of the present invention is solidified ink composition, can carry out the record that needs on recording medium.
In addition, use ink jet recording method of the present invention and/or ink-jet recording device of the present invention, can form the print of a part that is formed with image at least.Material to print is not particularly limited.
[embodiment]
The present invention is described in detail below to utilize embodiment, but the present invention is not limited by these.
(preparation of dispersible pigment dispersion)
Utilize the method pigment preparation dispersion liquid shown in following.
To as the C.I. Yan Liao of tinting material add as monomeric ethylene glycol-allyl ether (Japanese emulsifying agent corporate system among 7 (carbon black) 15 weight %, DiscolN-509 (the industrial's system of refining big day) the 3.5 weight % as dispersion agent.Hereinafter referred to as " AG "), be 100 weight % altogether, mix and stir, become mixture.Use sand mill (the peace river makes institute's corporate system), with this mixture of zirconium oxide bead (diameter 1.5mm) dispersion treatment 6 hours.Then, with separator separation of oxygenated zirconium pearl, De Dao dispersible pigment dispersion.
3), magenta pigment dispersion liquid (C.I. pigment violet 1 9), yellow pigment dispersion liquid (C.I. Pigment Yellow 73 155), dispersion liquid (C.I. Pigment white 6) in vain below similarly carry out, preparation and corresponding dispersible pigment dispersion of all kinds are green pigment dispersion liquid (C.I. pigment Blue 15:.
(preparation of ink composition A1～A6, ink composition B1～B14)
According to the preparation of the composition shown in following table 2～11 ink composition A1～A6.That is, from monomer, hyperbranched polymer, optical free radical polymerization starter, promoter, tensio-active agent, hot radical stopper, the composition weighing shown in the table, branch are got in the opacifying property container, utilized magnetic stirring apparatus, mix and dissolving fully.Then, add specified amount resin emulsion (Polymer Emulsion), mix and stirred 30 minutes.Then, filter each ink composition A1～A6, become the ink composition that needs with 5 μ m membrane filters.
Equally, according to the preparation of the composition shown in following table 2～11 and the table 13,14 ink composition B1～B14.That is, from monomer, hyperbranched polymer, promoter, tensio-active agent, hot radical stopper, the composition weighing shown in the table, branch are got in the opacifying property container, utilized magnetic stirring apparatus, mix and dissolving fully.Then, add the specified amount resin emulsion, mix and stirred 30 minutes.In solvent, drip lentamente when then, stirring described dispersible pigment dispersion.After dripping end, mix at normal temperatures and stirred 1 hour.Then, filter each ink composition B1～B14, become the ink composition that needs with 5 μ m membrane filters.Numeric representation in the table " weight % ".
As above-mentioned resin emulsion, use the system Laromer PE 46T of BASF AG, PE22WN, UA9029V.PE46T is a monomer dispersing type UV cured resin solvent, can disperse with the free-radical polymerised compound of following TPGDA and so on.PE22WN is an aqueous dispersion type UV cured resin solvent, can use water-dispersion.UA9029V is an organic solvent decentralized UV cured resin emulsion, can disperse with the organic solvent of butylacetate and so on.
TPGDA in the following table (tri (propylene glycol) diacrylate: be monomer the system Laromer TPGDA of BASF AG) with free-radical polymerised group.
In addition, ink composition A6, B10 are respectively the ink compositions that spent glycol one allyl ether (AG) displacement forms as the PE22WN of aqueous dispersion type UV cured resin emulsion in ink composition A2, B2.
In the present invention, as hyperbranched polymer, use " Viscoat#1000 ", " STAR-501 " of Osaka organic chemistry industry system.Be somebody's turn to do " Viscoat#1000 ", " STAR-501 " for being that center (core) makes functional group carry out the hyperbranched polymer of branching with the Dipentaerythritol, " Viscoat#1000 " is the material of the viscosity that contains glycol diacrylate as diluting monomer: 273mPas, functional group several 14 (acryl (acryl groups))." STAR-501 " is the material of the viscosity that contains dipentaerythritol acrylate as diluting monomer: 210Pas, functional group's several 20～99 (acryls).Outermost layer all has acryl (acryloyl groups), is fit to use.
In addition, because the stereoregularity height of branch-shape polymer, so the worker ordinal number is many, cost uprises, and the stereoregularity of hyperbranched polymer is so not high, is easier to synthesize, so the cost aspect is favourable.
(embodiment 1～11, comparative example 1)
The two-component-type combined light of using in embodiment 1～11, comparative example 1 is solidified the unitized construction of ink composition shown in following table 2～11.
Table 2
| Embodiment 1 | Embodiment 2 | |||
| Ink composition A1 | Ink composition B1 | Ink composition A1 | Ink composition B4 | |
| AG | 73.6 | 70.6 | 73.6 | 78.6 |
| TPGDA | 3.0 | 3.0 | 3.0 | - |
| STAR-501 | 10.0 | 12.0 | 10.0 | 14.0 |
| Polymer emulsion (PE 46T) | 7.0 | 7.0 | 7.0 | - |
| Irgacure 819 | 4.0 | - | 4.0 | - |
| Irgacure 127 | 1.0 | - | 1.0 | - |
| Darocur EHA | 1.0 | 1.0 | 1.0 | 1.0 |
| Pigment (C.I. pigment Bk7) | - | 6.0 | - | 6.0 |
| BYK-3570 | 0.2 | 0.2 | 0.2 | 0.2 |
| Irgastab UV-10 | 0.2 | 0.2 | 0.2 | 0.2 |
Table 3
| Embodiment 3 | Comparative example 1 | |||
| Ink composition | Ink composition | Ink composition | Ink composition | |
| A4 | B1 | A4 | B4 | |
| AG | 81.6 | 70.6 | 81.6 | 78.6 |
| TPGDA | - | 3.0 | - | - |
| STAR-501 | 12.0 | 12.0 | 12.0 | 14.0 |
| Polymer emulsion (PE 46 T) | - | 7.0 | - | - |
| Irgacure 819 | 4.0 | - | 4.0 | - |
| Irgacure 127 | 1.0 | - | 1.0 | - |
| Darocur EHA | 1.0 | 1.0 | 1.0 | 1.0 |
| Pigment (C.I. pigment Bk7) | - | 6.0 | - | 6.0 |
| BYK-3570 | 0.2 | 0.2 | 0.2 | 0.2 |
| Irgastab UV-10 | 0.2 | 0.2 | 0.2 | 0.2 |
Table 4
| Embodiment 4 | ||
| Ink composition A2 | Ink composition B2 | |
| AG | 73.6 | 70.6 |
| STAR-501 | 10.0 | 12.0 |
| Polymer emulsion (PE 22WN) | 5.0 | 5.0 |
| Irgacure 819 | 4.0 | - |
| Irgacure 127 | 1.0 | - |
| Darocur EHA | 1.0 | 1.0 |
| Pigment (C.I. pigment Bk7) | - | 6.0 |
| BYK-3570 | 0.2 | 0.2 |
| Irgastab UV-10 | 0.2 | 0.2 |
| Water | 5.0 | 5.0 |
Table 5
| Embodiment 5 |
| Ink composition A3 | Ink composition B3 | |
| AG | 73.6 | 70.6 |
| STAR-501 | 10.0 | 12.0 |
| Polymer emulsion (UA9029V) | 7.0 | 7.0 |
| Irgacure 819 | 4.0 | - |
| Irgacure 127 | 1.0 | - |
| Darocur EHA | 1.0 | 1.0 |
| Pigment (C.I. pigment Bk7) | - | 6.0 |
| BYK-3570 | 0.2 | 0.2 |
| Irgastab UV-10 | 0.2 | 0.2 |
| Butylacetate | 3.0 | 3.0 |
Table 6
| Embodiment 6 | ||
| Ink composition A1 | Ink composition B2 | |
| AG | 73.6 | 70.6 |
| TPGDA | 3.0 | - |
| STAR-501 | 10.0 | 12.0 |
| Polymer emulsion | 7.0(PE 46T) | 5.0(PE 22WN) |
| Irgacure 819 | 4.0 | - |
| Irgacure 127 | 1.0 | - |
| Darocur EHA | 1.0 | 1.0 |
| Pigment (C.I. pigment Bk7) | - | 6.0 |
| BYK-3570 | 0.2 | 0.2 |
| Irgastab UV-10 | 0.2 | 0.2 |
| Water | - | 5.0 |
Table 7
| Embodiment 7 | ||
| Ink composition A1 | Ink composition B3 | |
| AG | 73.6 | 70.6 |
| TPGDA | 3.0 | - |
| STAR-501 | 10.0 | 12.0 |
| Polymer emulsion | 7.0(PE46T) | 7.0(UA9029V) |
| Irgacure 819 | 4.0 | - |
| Irgacure 127 | 1.0 | - |
| Darocur EHA | 1.0 | 1.0 |
| Pigment (C.I. pigment Bk7) | - | 6.0 |
| BYK-3570 | 0.2 | 0.2 |
| Irgastab UV-10 | 0.2 | 0.2 |
| Butylacetate | - | 3.0 |
Table 8
| Embodiment 8 | ||
| Ink composition A2 | Ink composition B1 | |
| AG | 73.6 | 70.6 |
| TPGDA | - | 3.0 |
| STAR-501 | 10.0 | 12.0 |
| Polymer emulsion | 5.0(PE22WN) | 7.0(PE46T) |
| Irgacure 819 | 4.0 | - |
| Irgacure 127 | 1.0 | - |
| Darocur EHA | 1.0 | 1.0 |
| Pigment (C.I. pigment Bk7) | - | 6.0 |
| BYK-3570 | 0.2 | 0.2 |
| Irgastab UV-10 | 0.2 | 0.2 |
| Water | 5.0 | - |
Table 9
| Embodiment 9 | ||
| Ink composition A3 | Ink composition B1 | |
| AG | 73.6 | 70.6 |
| TPGDA | - | 3.0 |
| STAR-501 | 10.0 | 12.0 |
| Polymer emulsion | 7.0(UA9029V) | 7.0(PE46T) |
| Irgacure 819 | 4.0 | - |
| Irgacure 127 | 1.0 | - |
| Darocur EHA | 1.0 | 1.0 |
| Pigment (C.I. pigment Bk7) | - | 6.0 |
| BYK-3570 | 0.2 | 0.2 |
| Irgastab UV-10 | 0.2 | 0.2 |
| Butylacetate | 3.0 | - |
Table 10
| Embodiment 10 | ||
| Ink composition A5 | Ink composition B9 | |
| AG | 67.6 | 71.6 |
| Viscoat#1000 | 20.0 | 15.0 |
| Polymer emulsion | PE46T 7.0 | PE46T 7.0 |
| Irgacure 819 | 4.0 | - |
| Irgacure 127 | 1.0 | - |
| Pigment | - - | C.I. pigment Bk7 6.0 |
| BYK-3500 | 0.2 | 0.2 |
| Irgastab UV-10 | 0.2 | 0.2 |
Table 11
| Embodiment 11 | ||
| Ink composition A6 | Ink composition B10 | |
| AG | 78.6 | 75.6 |
| STAR-501 | 10.0 | 12.0 |
| Polymer emulsion (PE 22WN) | 5.0 | 5.0 |
| Irgacure 819 | 4.0 | - |
| Irgacure 127 | 1.0 | - |
| Darocur EHA | 1.0 | 1.0 |
| C.I. pigment Bk7 | - | 6.0 |
| BYK-3500 | 0.2 | 0.2 |
| Irgastab UV-10 | 0.2 | 0.2 |
(evaluation method)
[solidified nature test 1]
Be dropped on the glass substrate the ink composition A and the B as two-component-type combined light curing ink composition of preparation as mentioned above and mixing, as sample, carry out the evaluation that the two-component-type combined light is solidified the solidified nature of ink composition with following main points with it.As UV irradiation equipment, use the device that is made with the ultraviolet LED NICHIA i-LED " NCCU033 " of the long 365nm of spike and the ultraviolet LED NICHIA " NCCU001 " of the long 380nm of spike (being Ri Ya chemical industrial company system).The illuminate condition of UV irradiation equipment is that at shadow surface, the exposure intensity of 365nm and 380nm wavelength is respectively 30mW/cm
2, be 60mW/cm altogether
2Then, to sample irradiation ultraviolet ray in 5 seconds, the integration light quantity of at every turn implementing the uviolizing processing becomes 300mJ/cm
2Then, use following judgement criteria, carry out the visual valuation that the two-component-type combined light is solidified the oozing out of ink composition, edge of image portion.The result is as shown in table 12.
[oozing out evaluation]
AA: when ink composition solidifies, do not ooze out.
A: taken place to ooze out, do not had solidified liquid to ooze out, but in normal temperature, printing process required time inner drying, unquestioned level.
B: taken place to ooze out, do not had solidified liquid to ooze out, but placed 15 minutes dryings at normal temperatures.
C: taken place to ooze out, do not had solidified liquid to ooze out, do not had drying in 15 minutes but place at normal temperatures.
[visual valuation of edge of image portion]
AA: the border that can clearly differentiate printing portion and non-printing portion.
A: owing to ooze out and a part of colorant oozes out, but be the level on the border that can clearly differentiate printing portion and non-printing portion.
B: owing to ooze out and colorant oozes out, but, become the level of problem for the border of printing portion and non-printing portion thickens.
C: owing to ooze out and colorant oozes out, can not distinguish the border of printing portion and non-printing portion.
[stationarity]
Utilize the system ink-jet printer PM-G920 of Seiko Epson (Seiko Epson) Co., Ltd., the ink composition A1 of above-mentioned example is filled in light look (gloss optimizer) row, ink composition B1～B4 is filled in matte black (matte black) row, the OHP film of recording medium use A4 size (Xerox of Fuji (strain) system, XEROX FILM＜boundless 〉).Then, utilizing the described uviolizing light source that is arranged at ejection port, is 900mJ/cm with the integration light quantity
2Condition of cure carried out printing and solidification treatment, the cured coating film that obtains relatively uses Nichiban corporate system Cellotape (registered trademark) No.405, is with stripping test.And then, change ink composition A1 into A2, A3, A4, A5, A6 successively, and then except ink composition B1～4, also use B9, B10, carry out identical test.Evaluation result is as shown in table 12.
[band stripping test]
AA: does not peel off at the interface at cured coating film and film.
A: the part of the edge section of cured coating film is attached to the bonding coat of band and peels off, and is level that can be practical.
B: peel off at the interface at cured coating film and film, and the major part of cured coating film is attached to the bonding coat of band.
C: peel off at the interface at cured coating film and film, and whole being attached to of cured coating film is with and is stripped from.
Table 12
| Ink composition A | Ink composition B | Ooze out evaluation | Image border portion visual valuation | Stationarity is estimated | |
| Embodiment 1 | A1 | B1 | AA | AA | AA |
| Embodiment 2 | A1 | B4 | AA | AA | AA |
| Embodiment 3 | A4 | B1 | AA | AA | AA |
| Embodiment 4 | A2 | B2 | B | B | A |
| Embodiment 5 | A3 | B3 | A | A | A |
| Embodiment 6 | A1 | B2 | B | A | A |
| Embodiment 7 | A1 | B3 | A | A | A |
| Embodiment 8 | A2 | B1 | B | A | A |
| Embodiment 9 | A3 | B1 | A | A | A |
| Embodiment 10 | A5 | B9 | AA | AA | AA |
| Embodiment 11 | A6 | B10 | A | A | A |
| Comparative example 1 | A4 | B4 | AA | A | C |
[solidified nature test 2]
Use and respectively make up the color ink fluid composition shown in the following table 13, use ink composition A1 as ink composition A, use ink composition B1 as ink composition B, B5～B8, utilize the system ink-jet printer PM-G920 of Seiko Epson Corp, the ink composition B1 of above-mentioned example is filled in light black (photo black) row, each color ink liquid of ink composition B5～B7 is filled in corresponding colour row respectively, ink composition A1 is filled in light look (glossoptimizer) row, ink composition B8 is filled in matte black (matte black) row, at normal temperatures and pressures, cover at ink composition A1 under the print conditions in entire image zone, in the position of each color ink drop correspondence, implement the full-colour image printing.The OHP film of recording medium use A4 size (Xerox of Fuji (strain) system, XEROX FILM＜boundless 〉).Then, utilize the described uviolizing light source that is arranged at ejection port, become 900mJ/cm with the integration light quantity
2Condition of cure print and solidification treatment, affirmation can obtain not having the cured coating film of the full-colour image that oozes out.
Table 13
| Ink composition A1 | Ink composition B1 | Ink composition B5 | Ink composition B6 | Ink composition B7 | Ink composition B8 | |
| AG | 73.6 | 70.6 | 70.6 | 70.6 | 70.6 | 70.6 |
| TPGDA | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 |
| STAR-501 | 10.0 | 12.0 | 12.0 | 12.0 | 12.0 | 12.0 |
| Polymer emulsion (PE 46T) | 7.0 | 7.0 | 7.0 | 7.0 | 7.0 | 7.0 |
| Irgacure 819 | 4.0 | - | - | - | - | - |
| Irgacure 127 | 1.0 | - | - | - | - | - |
| Darocur EHA | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| Pigment | - | C.I. pigment Bk7 6.0 | C.I. pigment Blue 15: 3 6.0 | C.I. pigment violet 19 6.0 | C.I. Pigment Yellow 73 155 6.0 | C.I. Pigment white 6 6.0 |
| BYK-3570 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Irgastab UV-10 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
In addition, use and respectively make up the color ink fluid composition shown in the following table 14, use ink composition A5 as ink composition A, use ink composition B9 as ink composition B, B11～B14, utilize the system ink-jet printer PM-G920 of Seiko Epson Corp, the ink composition B9 of above-mentioned example is filled in light black (photo black) row, each color ink liquid of ink composition B11～B13 is filled in corresponding colour row respectively, ink composition A5 is filled in light look (gloss optimizer) row, ink composition B14 is filled in matte black (matte black) row, at normal temperatures and pressures, cover at ink composition A5 under the print conditions in entire image zone, in the position of each color ink drop correspondence, implement the full-colour image printing.The OHP film of recording medium use A4 size (Xerox of Fuji (strain) system, XEROX FILM＜boundless 〉).Then, utilize the described uviolizing light source that is arranged at ejection port, become 900mJ/cm with the integration light quantity
2Condition of cure print and solidification treatment, affirmation can obtain not having the cured coating film of the full-colour image that oozes out.
Table 14
| Ink composition | Ink composition | Ink composition | Ink composition | Ink composition | Ink composition |
| A5 | B9 | B11 | B12 | B13 | B14 | |
| AG | 67.6 | 71.6 | 71.6 | 71.6 | 71.6 | 71.6 |
| PVC ス コ one ト # 1000 | 20.0 | 15.0 | 15.0 | 15.0 | 15.0 | 15.0 |
| Polymer emulsion | PE 46T 7.0 | PE 46T 7.0 | PE 46T 7.0 | PE 46T 7.0 | PE 46T 7.0 | PE 46T 7.0 |
| Irgacure 819 | 4.0 | - | - | - | - | - |
| Irgacure 127 | 1.0 | - | - | - | - | - |
| Pigment | - | C.I. pigment Bk7 | C.I. pigment Blue 15: 3 | C.1. pigment violet 19 | C.I. Pigment Yellow 73 213 | C.I. Pigment white 6 |
| - | 6.0 | 6.0 | 6.0 | 6.0 | 6.0 | |
| BYK-3570 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Irgastab UV-10 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
From above result as can be known, ink composition A, the ink composition B that the two-component-type combined light of each embodiment among the present invention is solidified ink composition can obtain the result that satisfy in solidified nature and stationarity evaluation, can use fully.
Claims (23)
1. a two-component-type combined light is solidified ink composition, this ink composition comprises and contains optical free radical polymerization starter and free-radical polymerised compound at least and do not contain the ink composition A of colorant does not contain the optical free radical polymerization starter with containing colorant and free-radical polymerised compound at least ink composition B, it is characterized in that
In any one party or both sides, contain the resin emulsion that is scattered in the free-radical polymerised compound.
2. two-component-type combined light according to claim 1 is solidified ink composition, it is characterized in that,
Described ink composition A and B do not contain water.
3. two-component-type combined light according to claim 1 and 2 is solidified ink composition, it is characterized in that,
Described resin emulsion is the emulsion with resin of polymerizable group.
4. solidify ink composition according to any described two-component-type combined light in the claim 1～3, it is characterized in that,
As the free-radical polymerised compound of described ink composition A and/or described ink composition B, contain allylic compound and/or N-vinyl compound.
5. two-component-type combined light according to claim 4 is solidified ink composition, it is characterized in that,
What contain among described ink composition A and/or the described ink composition B contains allylic compound and/or the N-vinyl compound scope at 20 weight %～80 weight %.
6. solidify ink composition according to claim 4 or 5 described two-component-type combined light, it is characterized in that,
It is described that to contain allylic compound be ethylene glycol one allyl ether.
7. solidify ink composition according to claim 4 or 5 described two-component-type combined light, it is characterized in that,
Described N-vinyl compound is the N-vinyl formamide.
8. solidify ink composition according to any described two-component-type combined light in the claim 1～7, it is characterized in that,
Free-radical polymerised compound as described ink composition A and/or described ink composition B contains the branched chain type polymkeric substance.
9. two-component-type combined light according to claim 8 is solidified ink composition, it is characterized in that,
Described branched chain type polymkeric substance is branch-shape polymer and/or hyperbranched polymer.
According to Claim 8 or 9 described two-component-type combined light solidify ink compositions, it is characterized in that,
The concentration of described branched chain type polymkeric substance is 3 weight %～30 weight %.
11. solidify ink composition according to any described two-component-type combined light in the claim 1～10, it is characterized in that,
Described ink composition A and/or described ink composition B contain tensio-active agent.
12. two-component-type combined light according to claim 11 is solidified ink composition, it is characterized in that,
As described tensio-active agent, use polyether-modified polydimethylsiloxane or polyester modification polydimethylsiloxane.
13. solidify ink composition according to any described two-component-type combined light in the claim 1～12, it is characterized in that,
Described ink composition A and/or described ink composition B contain promoter.
14. two-component-type combined light according to claim 13 is solidified ink composition, it is characterized in that,
As described promoter, comprise more than any one of amine compound, thioxanthone, polymerizability particulate.
15. solidify ink composition according to any described two-component-type combined light in the claim 1～14, it is characterized in that,
The described optical free radical polymerization starter that contains among the described ink composition A is any one of alpha-amino group ketone, alpha-alcohol ketone, acylphosphine oxide.
16. solidify ink composition according to any described two-component-type combined light in the claim 1～14, it is characterized in that,
The described optical free radical polymerization starter that contains among the described ink composition A mixes and uses any more than 2 kinds of alpha-amino group ketone, alpha-alcohol ketone, acylphosphine oxide.
17. solidify ink composition according to any described two-component-type combined light in the claim 1～16, it is characterized in that,
Described ink composition A and/or described ink composition B contain the hot radical stopper.
18. two-component-type combined light according to claim 17 is solidified ink composition, it is characterized in that,
Described hot radical stopper is the HALS based compound.
19. solidify ink composition according to any described two-component-type combined light in the claim 1～18, it is characterized in that,
The described colorant that contains among the described ink composition B is a pigment.
20. an ink-jet is solidified ink composition with the two-component-type combined light, it is characterized in that,
Use any described two-component-type combined light curing ink composition in the claim 1～19.
21. an ink jet recording method is characterized in that,
Use the described ink-jet of claim 20 to solidify ink composition with the two-component-type combined light.
22. an ink-jet recording device is characterized in that,
Possess the described ink-jet of claim 20 and solidify ink composition with the two-component-type combined light.
23. a print is characterized in that,
Use described ink jet recording method of claim 21 and/or the described ink-jet recording device of claim 22 and form the part of image at least.
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| JP2006341809 | 2006-12-19 | ||
| JP2006341809 | 2006-12-19 | ||
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