CN101568553A - Novel radiation curable compositions - Google Patents

Abstract

A radiation curable composition comprising a curable compound, a photo-initiator and a co-initiator characterized in that said co-initiator is represented by Formula (I), wherein MA is the residue of a mono- or oligofunctional Michael acceptor; L is a divalent linking group positioning the two tertiary amines in a 1-3 to 1-10 position, with the proviso that both amines are aliphatic; R1, R2 and R3 independently represent an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group or an optionally substituted (hetero) alkaryl group; any two of R1, R2 and R3 may represent the necessary atoms to form a ring; any two of R1, R2 and R3 may represent the necessary atoms to form a ring with any of the atoms of the linking group L; n is an integer ranging from 1 to 6.

Description

The composition of novel radiation curable

Invention field

The present invention relates to contain the radiation-hardenable composition of novel coinitiator, described novel coinitiator can be used for radiation-hardenable composition, as varnish, jaqan (lacquer) and printing-ink (for example radiation-hardenable jetted ink).

Background of invention

Radiation-hardenable composition (for example radiation-hardenable jetted ink) comprises light trigger usually.When described composition exposed, light trigger caused the curing of described composition, i.e. polymerization.

Free radical photo-initiation can be divided into Norrish I type or Norrish II type light trigger.I type light trigger experience light fracture (photo-cleavage) is to produce free radical; And II type light trigger produces free radical by capturing process (most applications is for taking hydrogen by force).When I type light trigger produced free radical by the unit molecule bond cleavage reaction, II type light trigger formed free radical in the presence of second kind of molecule, and described second kind of molecule is so-called coinitiator, is also referred to as the polymerization synergistic agent.

First problem of radical polymerization process is that oxygen suppresses polymeric, and promptly curing speed reduces.The inhibition that oxygen causes not only causes overall curing speed to reduce, and causes solidifying inhomogeneous, and for example the surface cure difference causes surfaces of tacky.

Amine is well-known as the coinitiator of II type light trigger in the art, and it suppresses the oxygen quenching effect of radical polymerization process." the Radiation Curing in Polymer Science andTechnology; the 3rd volume " in for example R.S.Davidson, J.P.Fouassier etc., Elsevier Applied Science have been summarized in the effect of amine in curing system, 1993, the 153-176 pages or leaves.

When the coinitiator of remained unreacted in the curing composition, may occur with radiation-hardenable composition in second relevant problem of coinitiator (for example amine) of existing.Seldom quantitative from amine coinitiator to the hydrogen transference of II type light trigger.Unreacted coinitiator still can move in curing composition, and may influence the physical properties of curing composition unfriendly, perhaps may be diffused into outside the curing composition.If this radiation-hardenable composition is printed onto in the food product pack, then unreacted coinitiator (being also referred to as extractable content (extractable)) is extracted in the food, can produce Health hazard.A kind of method that obtains low extractable content can be to improve the reactivity of coinitiator, to avoid solidifying the unreacted coinitiator in back.What reduce unreacted coinitiator can be the another kind of method that obtains less extractable content to external diffusion.Thereby make coinitiator copolymerization when solidifying by making coinitiator have polymerizable groups; Perhaps, can realize reducing to external diffusion by improving the molecular weight of coinitiator.

US 3845056, US 3963771 disclose the amine acrylate (amine acrylates) that is produced by polyacrylic ester (preferred diacrylate) and the amine reaction with at least one hydrogen that links to each other with nitrogen-atoms with US 4045416.Described amine acrylate contains polymerizable groups, for radiation-curable coating composition provides curing speed fast.

EP-A 1147098 discloses has low viscous multifunctional reactive amines acrylate, and it prepares by multifunctional (methyl) acrylate and cyclic secondary amine reaction.These amine acrylate make that the radiation-hardenable composition curing speed is good, thermostability is higher and extractable content is less.

Disclose the novel amine coinitiator that makes up with I type and/or II type light trigger in WO 03/091288, described amine coinitiator is to have 10 trialkylamines to about 36 carbon atoms altogether, and wherein, the chain length of at least one alkyl is at least 8 carbon atoms.According to WO 03/091288, compare with commonly used amine (for example N-methyl-N, N-diethanolamine), when described amine coinitiator makes up with II type light trigger, after curing, provide less extractable content.

WO 99/07746 discloses a kind of radiation-hardenable composition, it comprises radiation curable resins, light trigger and as the amine of coinitiator, it is characterized in that, described amine is the compound that contains at least one uncle's amino, and at least one substituting group on wherein said uncle's amino is the aliphatic chain that contains at least one electron-withdrawing group.Described amine compound is preferably the dendrimer of the branching that contains at least one uncle's amino, highly branched or star.Described coinitiator and the combination of II type light trigger provide higher curing speed and less extractable content.

EP-A 1616922 discloses a kind of radiation-hardenable composition, it comprises radiation curable resins, light trigger and coinitiator, it is characterized in that, described coinitiator comprises and has at least one branch-shape polymer that causes functional group altogether nuclear, the described end group that causes functional group's (for example aliphatic amine or aromatic amine) as polymer core altogether.Be characterised in that according to the radiation-hardenable composition of EP-A 1616922 curing speed height and extractable content amount are low.

Yet the amount that reduces extractable content by the molecular weight that improves coinitiator may cause curable compositions to have too high viscosity.

The other problem relevant with curable compositions (particularly jetted ink) is photic jaundice (photoyellowing) and adheres to.

Photic jaundice is owing to light trigger and/or coinitiator decompose the variable color result who sees after curing.For the radiation curable ink of cyan that contains a large amount of isopropyl thioxanthone type light triggers and white, observe this photic jaundice especially easily, it produces general green cyan, the white of yellowing respectively in printing with after solidifying.The specific mixture that EP-A 0036075 and DE-A 3126433 disclose light trigger carries out photopolymerization to obtain being characterised in that the purposes in the extremely low polymkeric substance of yellowing at ethylenically unsaturated compounds.

Compare with the water-based inks that absorptivity printing ink receives on the body (ink-receiver), find substantially not absorptivity printing ink receive the character of the UV curing inks on the body and interact very complicated.Especially, good and controlled the sprawling that receives printing ink on the body at printing ink proves in-problem, and observes sticking problem when adopting dissimilar not absorptivity printing ink to receive body.A kind of method that addresses these problems is for dissimilar base material exploitations and uses different printing ink group (ink set), but because it is very consuming time to change printing ink in printer and print head, and it neither really feasible settling mode for industrial printing environment, so this is not a kind of preferred settling mode.Adopt different polymerizable compound, tensio-active agent, binding agent and/or organic solvent can influence adhesivity.US 6814791 discloses ink jet printing method, wherein, will contain methyl acetate and be printed onto on propylene and the ethene base material (substrate) as the ink composite of solvent.The suitable solvent of selecting of use causes the local swelling (swelling) or the dissolving of substrate surface usually, produces better adhesivity like this, still owing to the evaporation of solvent, also can cause the problem of the spray nozzle clogging of print head.Known to using one or more to be suitable for swelling polyvinyl chloride (PVC) base material, and when being selected from the monomer of tetrahydrofurfuryl acrylate, 1,6 hexanediol diacrylate and N-caprolactam, also can promote the adhesion of radiation curable ink on the PVC base material.Yet, when using one or more to be suitable for the swelling polycarbonate substrate and to be selected from the monomer of vinylformic acid 2-phenoxy ethyl, vinylformic acid 2-(2-ethoxy ethoxy) ethyl ester and polyethyleneglycol diacrylate, promote the adhesion on polycarbonate substrate.Therefore, must preparation be fit to polyvinyl chloride base material and polycarbonate substrate swollen " best possible " monomer mixture.Frequently, such mean method--by preparing the complex mixture of various compositions, receive at several printing ink by this and obtain on the bodies that acceptable adhesivity--the dispersion stabilization to painted jetted ink has negative impact.Adhesion issues is also relevant with the contraction of ink lay behind the radiation curing.At this on the one hand, compare with free radical polymerizable printing ink, it is excellent that cationic ink is considered to.EP-A 1705229 discloses the cationically polymerizable jetted ink that demonstrates good adhesivity and package stability.US 6310115 discloses and has contained the monomeric radiation-hardenable inkjet ink composition of radiation-hardenable, and described monomer comprises vinyl ether and acrylate-functional groups, and it can solidify by cationoid polymerisation and radical polymerization.In the free radical jetted ink, think that a large amount of monofunctional acrylates helps adhering to.EP-A 1668084 and US 7104642 address adhesivity, and disclose the jetted ink of radiation-hardenable, and it is the above monofunctional acrylate compounds of 65 quality % that this jetted ink contains quantity.As jetted ink being carried out improved substituting, the surface chemistry that printing ink is received body is modified and is become common method, and described modification is that so-called priming paint (primer) carries out by pre-treatment such as Cement Composite Treated by Plasma or corona treatment or by using suitable upper layer.Corona discharge Treatment and Cement Composite Treated by Plasma have increased cost, complicacy and the maintenance cost of the device that is used to handle substrate.Substrate may comprise a large amount of impurity or irregularity, and they may hinder the processing to substrate, and therefore can not bring the uniformly dispersing and the adhesivity of printing ink.Another kind of possibility is an application of primer before spraying jetted ink.Usually, before spraying jetted ink, upper layer is coated with and dry or curing, for example in the ink jet printing process in EP-A 1671805 and US 2003021961; But as in WO 00/30856, also can keep moistening, uncured upper layer.

Goal of the invention

The purpose of this invention is to provide radiation-hardenable composition, it contains and Norrish I type light trigger or Norrish II type light trigger or the combined novel coinitiator of a class of their combination, described composition has acceptable viscosity, high curing rate and low levels extractable content, and the latter provides the possibility of carrying out ink jet printing in food product pack.

Another object of the present invention provides the novel coinitiator of a class of easy acquisition.

Another purpose of the present invention provides curable composition, it is characterized in that yellowing is low, and improves the adhesivity on (more especially at polyolefine) on the plastic basis material.

According to following description, these purposes of the present invention and other purpose will become apparent.

Summary of the invention

Known in this field, aliphatic amine and aromatic amine are as the coinitiator of II type light trigger.

We find, make the curable compositions that comprises I type or II type light trigger or their combination have high curing rate according to the amine coinitiator of formula I.In addition, described coinitiator makes curable compositions have the extractable content of acceptable viscosity and low amount.

Formula I

Described new kind coinitiator can carry out well-known Michael reaction with secondary amine and acquisition easily by single functionality or low functionality michael acceptor (mono-or oligofunctional Michael acceptor), and described secondary amine comprises at least a other aliphatic tertiary amine in its structure.

Described new kind coinitiator also makes the less jaundice of curable compositions, and improves its adhesion on plastic basis material.

The preferred embodiment of the present invention limits in independent claim.

Detailed Description Of The Invention

Radiation-hardenable composition contains at least three kinds of components: (i) curable compound, (ii) light trigger and (iii) coinitiator.Described composition can further contain: one or more stoppers (inhibitor), tensio-active agent, tinting material, dispersion agent or dispersion synergists (dispersionsynergist).Described radiation-hardenable composition is preferably the radiation-hardenable jetted ink, more preferably the UV-curable jetted ink.

Coinitiator

Coinitiator according to the present invention has the structure according to formula I,

Formula I

Wherein, MA is the residue of single functionality or low functionality michael acceptor;

L is a divalent linking group, and it is positioned two kinds of tertiary amines for the 1-3 position to the 1-10 position, and condition is that two kinds of amine are aliphatic amine;

R1, R2 and R3 represent the optional alkyl that replaces, the optional thiazolinyl that replaces, the optional alkynyl that replaces or optional (mixing) alkaryl that replaces independently;

Any two the essential atoms that can represent to form ring among R1, R2 and the R3;

Any two the essential atoms that can represent to form ring among R1, R2 and the R3 with the arbitrary atom of linking group L;

N is the integer of 1-6.

Aliphatic amine refers to that wherein all substituting groups are the amine of aliphatic series or comprise amine with the direct-connected aliphatic group of nitrogen of amine.Described substituting group can comprise the aromatic series part, and condition is that this aromatic series part directly is not connected (for example alkaryl) with the nitrogen of amine.

Divalent linker L contains at least one carbon atom.The divalent linker L that comprises a carbon atom is positioned two kinds of tertiary amines for the 1-3 position.Divalent linker L is preferably aliphatic C2 to C6 divalent linker.

Divalent linker L is positioned two kinds of tertiary amines for the 1-3 position to the 1-10 position, and preferred orientation to the 1-8 position, more preferably is positioned the 1-3 position to the 1-6 position in the 1-3 position.

The alkyl of mentioning among the formula I is meant all possible variant for the carbon atom of each number in the alkyl, that is to say for 3 carbon atoms to be: n-propyl and sec.-propyl; To 4 carbon atoms be: normal-butyl, isobutyl-and the tertiary butyl; For 5 carbon atoms be: n-pentyl, 1,1-dimethyl-propyl group, 2,2-dimethyl propyl and 2-methyl-butyl etc.

Preferably, R1, R2 and R3 represent C1 to C5 alkyl independently.

Another preferred embodiment in, R2 and R3 represent to form the essential atom of 5 or 6 yuan of rings.Another preferred embodiment in, R1 and R2 represent that the atom with linking group L forms the essential atom of optional 6 yuan of rings that replace.

Coinitiator according to formula I is the reaction product of single functionality or low functionality michael acceptor and secondary amine, and described amine contains at least a other aliphatic tertiary amine in its structure.Nucleophilic compound (for example secondary amine) and 1 of activity double key (being also referred to as michael acceptor), the 4-addition is considered to Michael reaction.When two keys were replaced by at least one electron-withdrawing group, being considered to this pair key was activity double key or michael acceptor.Preferred electron-withdrawing group is selected from nitrile, ester, acid amides, sulphonamide, sulphonate (sulfonate), sulfone, sulfoxide, phosphonic acid ester (phosphonate), aldehyde and ketone.The nucleophilic addition(Adn) of secondary amine on activity double key is the representative instance of 1,4 Michael reaction.

Amine cannot be primary amine, to avoid the polycondensation between this primary amine and the michael acceptor.

The functionality of the Integer n reflection michael acceptor among the formula I: for single functionality michael acceptor, n=1; For two functionality michael acceptors, n=2 etc.

The amount of used amine and the functionality of michael acceptor adapt in coinitiator synthetic.

According to a kind of embodiment, the amount by making amine and the functionality of michael acceptor adapt, the coinitiator of the present invention that is not comprised polymerizable groups: when using the single functionality michael acceptor,, use about 1 normal amine for the michael acceptor of monovalent; When using two functionality michael acceptors,, use about 2 normal amine for the michael acceptor of monovalent; Or the like.

According to another kind of embodiment, the amount by making amine and the functionality of michael acceptor adapt, obtain containing the coinitiator of the present invention of ethylenic unsaturated polymerizable group: under the situation of tetravalence michael acceptor, when using about 2 normal amine, produce coinitiator with two polymerizable groups.Be preferably acrylate-basedly according to the ethylenic unsaturated polymerizable group of the coinitiator of this embodiment, for example, michael acceptor is preferably acrylate.Have been found that the coinitiator of the present invention that contains ethylenic unsaturated polymerizable group (preferred acrylate base), improve the adhesion of curable compositions on plastic basis material (more especially such as polyacrylic polyolefine).Also have been found that the also pKa value relevant (referring to following) of the secondary amine used with preparing coinitiator of adherent improvement: pKa is high more, and then the adhesivity of coinitiator is improved.Yet, according to present embodiment, have the coinitiator of high pKa, have the trend of the colloidal stability of negative impact radiation curable ink, this depends on used dispersion agent.Have been found that when the pKa value for preparing the used secondary amine of coinitiator is between 7.0 and 9.5, can realize the optimum balance between adhesion property and the colloidal stability.Therefore, especially preferably contain the coinitiator of piperazine or morpholine part, it has the pK of typical aromatic series coinitiator (as 4-dimethylamino-ethyl benzoate) _aPK with aliphatic coinitiator (for example Craynor CN386 well known in the prior art) _aBetween middle pK _a, it demonstrates optimum balance between adhesion property and colloidal stability.

Secondary amine

Preparing in the coinitiator of the present invention used secondary amine contains at least a other tertiary amine and is represented by formula II

Formula II

Wherein L ' is a divalent linker, and it is positioned secondary amine and tertiary amine for the 1-3 position to the 1-10 position, and condition is that two kinds of amine are aliphatic amine;

R4, R5 and R6 represent the optional alkyl that replaces, the optional thiazolinyl that replaces, the optional alkynyl that replaces or optional (mixing) alkaryl that replaces independently;

Any two the essential atoms that can represent to form ring among R4, R5 and the R6;

Can represent any former with linking group L ' for any two among R4, R5 and the R6 in the essential atom that forms ring.

Divalent linker L ' contains at least one carbon atom.The divalent linker L ' that comprises a carbon atom is positioned secondary amine and tertiary amine for the 1-3 position.

Divalent linker L ' is preferably aliphatic C2 to C6 divalent linker.

Divalent linker L ' is positioned secondary amine and tertiary amine for the 1-3 position to the 1-10 position, and preferred orientation to the 1-8 position, more preferably is positioned the 1-3 position to the 1-6 position in the 1-3 position.

The alkyl of mentioning among the formula II is meant all possible variant of the carbon atom of each number in the alkyl, that is to say, for 3 carbon atoms is: n-propyl and sec.-propyl; For 4 carbon atoms be: normal-butyl, isobutyl-and the tertiary butyl; For 5 carbon atoms be: n-pentyl, 1,1-dimethyl-propyl group, 2,2-dimethyl propyl and 2-methyl-butyl etc.

Preferably, R4, R5 and R6 represent C1 to C5 alkyl independently.

In another preferred embodiment, R5 and R6 represent to form the essential atom of 5 or 6 yuan of rings.Another preferred embodiment in, R4 and R5 represent that the atom with linking group L ' forms the essential atom of optional 6 yuan of rings that replace.

In addition preferred embodiment in, contain two kinds of tertiary amines according to the secondary amine of formula II.

Some examples in table 1, have been provided according to the secondary amine of formula II.

Table 1

Michael acceptor

Michael acceptor is selected from: (methyl) acrylate ((meth) acrylates), (methyl) acrylamide, vinyl sulphone, vinylphosphonate (vinyl phosphonates), vinyl sulfonic acid ester (vinyl sulfonates), vinyl sulphonamide, maleimide, vinyl nitrile, vinyl ketone, vinyl aldehyde and vinyl sulfoxide.

Preferred michael acceptor is acrylate, methacrylic ester or vinyl sulphone.Michael acceptor can for single functionality or polyfunctionality, michael acceptor is preferably at least two functionality.

Some examples of michael acceptor have been provided in the table 2.

Table 2

Provided some specific exampless according to the coinitiator of one embodiment of the present invention in the table 3, wherein said coinitiator does not contain polymerizable groups.

Table 3

Provided some specific exampless according to the coinitiator of another embodiment of the invention in table 4, wherein said coinitiator has polymerizable groups.

Table 4

Further preferred coinitiator is the coinitiator according to formula III,

Formula III

Wherein R7, R8 and R9 represent the optional alkyl that replaces, the optional thiazolinyl that replaces, the optional alkynyl that replaces or optional (mixing) alkaryl that replaces independently;

R10 is hydrogen or methyl;

X represents-SO ₂-or-C (O)-O-;

L " expression contains the aliphatic divalent linker of 2 to 6 carbon atoms;

A represents two functionality or polyfunctionality linking group, and wherein maximum functionality is 6;

M is selected from hydroxyl or (methyl) acrylate group;

N is the integer of 2-6;

M is the integer of 0-4, and condition is that n+m is not more than 6.

Other preferred coinitiator has the structure according to formula IV,

Formula IV

Wherein R7, R8, R9, R10, L ", A, M, n and m have with formula III in identical implication.

Other preferred coinitiator has the structure according to formula V,

Formula V

Wherein R7, R8, R9, L ", A and n have with formula III in identical implication.

Radiation-hardenable composition can contain two or more different coinitiators of the present invention; Perhaps contain the combination of one or more coinitiators of the present invention and one or more other coinitiators known in the art.The example of one or more other coinitiators is: (1) aliphatic tertiary amine, for example methyldiethanolamine, dimethylethanolamine, trolamine, triethylamine and N-methylmorpholine; (2) aromatic amine, for example ESCAROL 507 pentyl ester, the positive fourth oxygen of 2-ethyl-4-(dimethylamino) benzoic ether, 2-(dimethylamino) ethylamino benzonitrile acid esters, ethyl-4-(dimethylamino) benzoic ether and 2-ethylhexyl-4-(dimethylamino) benzoic ether; (3) amine of (methyl) acroleic acid esterification ((meth) acrylated amine), for example (methyl) propenoic acid dialkyl aminoalkyl ester (for example vinylformic acid lignocaine ethyl ester) or N-morpholino alkyl-(methyl) acrylate (for example N-morpholino ethyl-acrylate); And (4) acid amides or urea.Preferably, the combination of coinitiator of the present invention and Aminobenzoate type coinitiator (for example ethyl-4-dimethylaminobenzoic acid ester).Particularly preferably be coinitiator of the present invention and combination available from Genocure EPD and the Genopol AB-1 of Rahn AG.Also particularly preferably be the combination of disclosed coinitiator among coinitiator of the present invention and unpub EP-A 06124637 and EP-A 06124635 (all filing an application) and the EP-A 06126800 (filing an application) at 2006-12-21 at 2006-11-23.

Coinitiator total amount in the radiation-hardenable composition with respect to the gross weight of described curable compositions, is preferably 0.01～20 weight %, and more preferably 0.05～15 weight % most preferably is 0.1～10 weight %.

Light trigger

Radiation-hardenable composition of the present invention contains one or more light triggers.When described composition exposes, the common initiated polymerization of light trigger.Once absorbing described radiation, light trigger produces free radical, thereby induces the polymerization of the curable compound (monomer, oligopolymer or (in advance) polymers) of described composition.When polyfunctional monomer or oligopolymer existed as curable compound, described free radical also can cause crosslinked.

Light trigger can be Norrish I type light trigger, Norrish II type light trigger or their combination.

Preferred Norrish I type-initiator is selected from benzoin ether, benzil ketals, α, α-dialkoxy-methyl phenyl ketone, Alpha-hydroxy alkyl phenones (phenone), alpha-aminoalkyl benzophenone, acylphosphine oxide, acyl group phosphine sulfide, α-Lu Daitong, alpha-halogen sulfone and oxoethanoic acid alpha-halogen phenyl ester.Preferred especially acylphosphine oxide or diacyl phosphine oxide.

Preferred Norrish II type-initiator is selected from benzophenone, thioxanthone, 1,2-diketone and anthraquinone.

Suitable I type and II type light trigger are disclosed in Wiley/SITA Series In Surface Coatings Technology III volume by people such as J.V.Crivello: " be used for the photopolymerisable light trigger of free radical, positively charged ion and negatively charged ion; the 2nd edition (Photoinitiators forFree Radical, Cationic﹠amp; Anionic Photolymerisation 2 ^NdEdition) " in, G.Bradley writes, and publishes the 276-294 page or leaf by John Wiley and Sons Ltd London in 1998.

The specific examples of light trigger includes but not limited to following compound or their combination: the benzophenone of benzophenone and replacement; the 1-hydroxycyclohexylphenylketone; thioxanthone (for example isopropyl thioxanthone); 2-hydroxy-2-methyl-1-phenyl third-1-ketone; 2-benzyl-2-dimethylamino-(4-morpholino phenyl) fourth-1-ketone; the benzil dimethyl ketal; two (2; the 6-dimethylbenzoyl)-2; 4; 4-tri-methyl-amyl phosphine oxide; 2; 4; 6-trimethylbenzoyl diphenyl phosphine oxide; 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino third-1-ketone; 2; 2-dimethoxy-1; 2-phenylbenzene second-1-ketone or 5,7-two iodo-3-butoxy-6-fluorones.

Suitable commodity light trigger comprises: can be from Irgacure 184, Irgacure 500, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 127, Irgacure 1700, Irgacure 651, Irgacure 819, Irgacure 1000, Irgacure 1300, Irgacure 1870, Darocur 1173, Darocur2959, Darocur 4265 and the Darocur ITX of CIBA SPECIALTY CHEMICALS acquisition; Can be from the LucerinTPO of BASF AG acquisition; Can be from Esacure KT046, Esacure KIP150, Esacure KT37 and the Esacure EDB of LAMBERTI acquisition; Can be from the H-Nu 470 and the H-Nu 470X of SPECTRA GROUP Ltd. acquisition; And can be from the Genopol TX-1 of Rahn AG acquisition.

Because light trigger produces free radical once absorbing radiation, therefore usually according to being used to make curable compositions solidified emission types to come the selective light initiator.If use two or more types radiation to solidify radiation-hardenable composition, then can there be two or more types light trigger.

With respect to the gross weight of radiation-hardenable composition, the preferred amounts of initiator be preferably 0.3～50 weight %, more preferably 1～25 weight %, most preferably be 2～15 weight %.

Radiation-hardenable composition can comprise one or more sensitizing agents.When described composition exposed, sensitizing agent can shift energy and cause free radical to form to light trigger.Suitable sensitizing agent comprises: photoreduction xanthene, fluorenes, benzodiphenylene oxide, benzothioxanthene, thiazine, oxazine, tonka bean camphor, pyronin, porphyrin, acridine, azo, diazonium, cyanine, merocyanine, diaryl methyl, triaryl methyl, anthraquinone, phenylenediamine, benzoglyoxaline, fluorescence dye, quinoline, tetrazolium, naphthols, p-diaminodiphenyl, rhodamine, indigo and/or indanthrene dye.

With respect to the gross weight of described curable compositions, the amount of sensitizing agent is preferably 0.01～15 weight %, 0.05～5 weight % more preferably.

Radiation-hardenable composition

Coinitiator of the present invention can be used for any radiation-hardenable composition, but for example coating composition spray composition, printing-ink, varnish, jaqan (lacquer), binder composition, functional fluid, for example conductive fluid (conductive fluid).

In preferred embodiment, curable compositions is a coating composition.Described coating composition can be used for having the coating layer of dissimilar functions, for example image recording layer (for example being used to receive the image of ink jet printing), priming paint, varnish and jaqan.

In another preferred embodiment, curable compositions is printing-ink or fluid.Printing-ink contains at least a tinting material, and printing fluids is essentially colourless.

Printing-ink or fluid can be any type well known in the art, for example: flexible ink (flexo ink), silk-screen ink (screen ink) or flexographic ink (offset ink), but be preferably jetted ink or fluid, most preferably be UV-curable printing ink or fluid.

Jetted ink or fluid can be used for perhaps can being used as functional fluid in the multicolor printing application, and this functional fluid is used to spray conductive layer, indicating meter, biology and medical fluid, optical fluid etc.

Use for multicolor printing, depend on ink jet printing method, can in one or more radiation-hardenable compositions, add coinitiator of the present invention.

Ink jet printing method comprises at least one ink-jet step, but can comprise one or more ink-jet steps, can also comprise one or more additional steps, for example coating step or lamination step.

Coinitiator of the present invention for example can be added in the composition as priming paint, one or more colored inks, varnish or jaqan.

Coinitiator of the present invention can be joined at least a colored ink, be restricted with the amount of guaranteeing extractable content.Therefore, preferably coinitiator of the present invention is joined in all printing ink of ink-jet ink set.

The advantage of coinitiator of the present invention is, only has the minute quantity extractable content can be from extracting the solidified ink lay.Therefore, in priming paint, use coinitiator of the present invention to be used on the permeable base substrate and spray, so that be can be on the base material from the compound formation blocking layer of the migration of the composition on the priming paint.Coinitiator also can be used for spraying (jettable) fluid, and forming the solidified supercoat, it prevents that the compound in the following curing composition from moving to material surface.

Except above-mentioned light trigger and coinitiator, the jetted ink of radiation-hardenable further contains radiation curable compounds and preferred at least a tinting material, for example pigment or dyestuff.Inkjet fluids does not contain tinting material.The jetted ink of radiation-hardenable can further contain one or more dispersion agents, dispersion synergists, stopper, tensio-active agent.

At 100s ^-1Shearing rate and 25～70 ℃ ink-jet temperature under, the viscosity of curable inkjet printing ink preferably is lower than 35mPa.s, more preferably less than 15mPa.s, most preferably is between 2 to 10mPa.s.

Curable pigment inkjet ink does not preferably comprise volatile component, can be favourable but introduce a spot of organic solvent sometimes in described printing ink, improves the adhesivity that receives the surface with printing ink so that solidify the back at UV.In this case, the solvent that is added can be any amount in the scope that can not cause solvent resistance and VOC problem, and with respect to the gross weight of curable pigment inkjet ink, it is preferably at 0.1-10.0 weight %, more preferably at 0.1-5.0 weight %.

Curable compound

Curable compound is generally monomer, oligopolymer, prepolymer or their combination.

Monomer, oligopolymer and/or prepolymer contain one, two, three or more polymerizable groups.Can use the mixture of monomer, oligopolymer and/or prepolymer with different quantities polymerizable groups.

By changing the ratio of monomer and oligopolymer, the viscosity that can regulate curable compositions.

Can use any polymerizable compound well known in the art.What be preferably used as radiation curable compounds especially in the jetted ink of radiation-hardenable is simple function and/or polyfunctional acrylic ester monomer, oligopolymer or prepolymer, for example: the vinylformic acid isopentyl ester, octadecyl acrylate, lauryl acrylate, Octyl acrylate, decyl acrylate, vinylformic acid isopentyl ester (isoamylstylacrylate), the different stearyl ester of vinylformic acid, vinylformic acid 2-ethylhexyl-glycol ether ester, vinylformic acid 2-hydroxyl butyl ester, 2-acryloxy ethyl hexahydrophthalic acid, vinylformic acid butoxy ethyl ester, vinylformic acid ethoxydiglycol ester, vinylformic acid methoxyl group glycol ether ester, vinylformic acid methoxy poly (ethylene glycol) ester, vinylformic acid MPEG ester, the vinylformic acid phenoxy ethyl, tetrahydrofurfuryl acrylate, isobornyl acrylate, vinylformic acid 2-hydroxy methacrylate, vinylformic acid 2-hydroxy propyl ester, vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester, the vinyl ether acrylate, 2-acryloxy ethyl succsinic acid, 2-acryloxy ethyl phthalic acid, 2-acryloxy ethyl-2-hydroxyethyl-phthalic acid, interior ester modified flexibility (flexible) acrylate, vinylformic acid tertiary butyl cyclohexyl, the diacrylate triethyleneglycol ester, diacrylate Tetraglycol 99 ester, the diacrylate macrogol ester, dipropylene glycol diacrylate, diacrylate tripropylene glycol ester, diacrylate polypropylene glycol ester, diacrylate 1, the 4-butanediol ester, diacrylate 1,6-hexylene glycol ester, diacrylate 1,9-nonanediol ester, diacrylic acid pentyl diol ester, dihydroxymethyl-tristane diacrylate, dihydroxyphenyl propane EO (oxyethane) affixture diacrylate, dihydroxyphenyl propane PO (propylene oxide) affixture diacrylate, hydroxy new pentane acid ester neopentylglycol diacrylate (hydroxypivalate neopentyl glycoldiacrylate), ethoxylated neopentylglycol diacrylate, alkoxylate dihydroxymethyl tristane diacrylate and diacrylate polytetramethylene glycol ester, Viscoat 295, the Viscoat 295 of EO modification, three vinylformic acid three (propylene glycol) esters, the Viscoat 295 of caprolactone modification, pentaerythritol triacrylate, pentaerythritol tetracrylate, tetrapropylene acid tetramethylolmethane ethoxylated ester, six vinylformic acid dipentaerythritol ester, two (TriMethylolPropane(TMP)) tetraacrylate, six vinylformic acid dipentaerythritol ester of glycerine propoxy-triacrylate and hexanolactam modification; Perhaps N-vinylamide, for example N-caprolactam or N-vinyl formamide; The perhaps acrylamide of acrylamide or replacement, for example acryloyl morpholine.

Other suitable monofunctional acrylate comprises: caprolactone acrylate, cyclic trimethylolpropane formal acrylate, ethoxylated nonylphenol acrylate, isodecyl acrylate, Isooctyl acrylate monomer, vinylformic acid octyl group ester in the last of the ten Heavenly stems, alkoxylate phenol acrylate, tridecyl acrylate and alkoxylate pimelinketone dimethanol diacrylate.

Other two suitable functional acrylates comprise: alkoxylate pimelinketone dimethanol diacrylate, alkoxylate hexanediyl ester, diox omega-diol diacrylate, diox omega-diol diacrylate, pimelinketone dimethanol diacrylate, diacrylate glycol ether ester and new diacrylate pentadiol ester.

Other suitable trifunctional acrylate comprises: propoxylated glycerol triacrylate and propoxylation Viscoat 295.

Other more the high functionality acrylate comprise: two-trimethylolpropane tetra-acrylate, Dipentaerythritol five acrylate, ethoxylation tetramethylol methane tetraacrylate, methoxylation EDIA and esters of acrylic acid.

In addition, can use with these acrylate with the corresponding methacrylic ester of aforesaid propylene acid esters.In these methacrylic esters, methoxy polyethylene glycol methacrylate-styrene polymer, methoxyl group triglycol methacrylic ester, methacrylic acid hydroxyl ethyl ester, methacrylic acid phenoxy ethyl, cyclohexyl methacrylate, tetraethylene glycol dimethacrylate and polyethylene glycol dimethacrylate, because they have high relatively sensitivity and higher to the adhesivity of printing ink reception surface, so preferred.

In addition, jetted ink can also comprise polymerizable oligomers.The example of these polymerizable oligomerses comprises: epoxy acrylate, aliphatic urethane acrylate, aromatic urethane acrylate, polyester acrylate and straight acrylics oligopolymer.

The suitable example of distyryl compound is: vinylbenzene, p-methylstyrene, to methoxy styrene, Beta-methyl vinylbenzene, to methyl-Beta-methyl vinylbenzene, alpha-methyl styrene and to methoxyl group-Beta-methyl vinylbenzene.

The suitable example of vinyl naphthalene compound is: 1-vinyl naphthalene, Alpha-Methyl-1-vinyl naphthalene, Beta-methyl-1-vinyl naphthalene, 4-methyl isophthalic acid-vinyl naphthalene and 4-methoxyl group-1-vinyl naphthalene.

The suitable example of N-vinyl compound is: N-vinylcarbazole, N-vinyl pyrrolidone, N-vinyl indoles, N-vinyl pyrrole, N-vinyl thiodiphenylamine, N-vinyl Acetanilide, N-vinyl ethyl acetamide, N-vinyl succinimide, N-vinyl phthalic imidine, N-caprolactam and N-vinyl imidazole.

Example with vinyl ethers of at least one vinyl ether group comprises: ethyl vinyl ether, n-butyl vinyl ether, IVE, octadecyl vinyl ether, cyclohexyl vinyl ether, the butyleneglycol divinyl ether, the hydroxybutyl vinyl ether, the cyclohexanedimethanol mono vinyl ether, Vinyl phenyl ether, the p-methylphenyl vinyl ether, the p-methoxyphenyl vinyl ether, the Alpha-Methyl Vinyl phenyl ether, Beta-methyl-IVE and β-chlorine IVE, diethylene glycol divinyl ether, triethylene glycol divinyl ether, n-propyl vinyl ether, isopropyl-ethylene base ether, dodecyl vinyl, the diglycol monotertiary vinyl ether, the cyclohexanedimethanol divinyl ether, phenylformic acid 4-(vinyloxy group) butyl ester, two [4-(vinyloxy group) butyl] esters of hexanodioic acid, two [4-(vinyloxy group) butyl] esters of succsinic acid, 4-(vinyloxy group methyl) cyclohexyl-methyl benzoic acid ester, two [4-(vinyloxy group) butyl] isophthalic ester, two [4-(vinyl-oxygen ylmethyl) cyclohexyl methyl] glutarate, three [4-(vinyloxy group)-butyl] trimellitate, 4-(vinyloxy group) butyl stearate, two [4-(vinyloxy group)-butyl] dihexyl double carbamate, two [4-(vinyloxy group) methyl]-cyclohexyl] methyl] terephthalate, two [4-(vinyloxy group) methyl] cyclohexyl] methyl] isophthalic ester, two [4-(vinyloxy group) butyl] (4-methyl isophthalic acid, the 3-phenylene)-double carbamate, two [the 4-vinyloxy group) butyl] (methylene radical two-(4, the 1-phenylene)) double carbamate, and 3-amino-1-propyl alcohol vinyl ether.

The monomer and the oligopolymer that can be used for the preferred kind of curable compositions are the vinyl ether acrylate, for example those compounds of describing among the US 6310115.Particularly preferred compound is vinylformic acid 2-(2-vinyloxy group oxyethyl group) ethyl ester and vinylformic acid 2-(2-vinyloxy group oxyethyl group) ethyl ester.

Tinting material

The radiation-hardenable jetted ink preferably comprises at least a tinting material.Tinting material can be a dyestuff, but preferably pigment or its combination.Pigment can also be the lake with at least one hydroxy-acid group or its salt.

Pigment can be black, white, cyan, magenta, yellow, redness, orange, purple, blueness, green, brown, their mixture etc.

Pigment can be selected from by HERBST, people such as Willy, " industrial pigment dyestuff, preparation, performance, application (Industrial Organic Pigments; Production; Properties, Applications) ", the 3rd edition, Wiley-VCH, 2004 (ISBN 3527305769) those disclosed.

Particularly preferred pigment is: C.I. Pigment Yellow 73 1,3,10,12,13,14,17,55,65,73,74,75,83,93,97,109,111,120,128,138,139,150,151,154,155,175,180,181,185,194 and 213.

Particularly preferred pigment is: C.I. Pigment red 17,22,23,41,48:1,48:2,49:1,49:2,52:1,57:1,81:1,81:3,88,112,122,144,146,149,169,170,175,176,184,185,188,202,206,207,210,216,221,248,251,254,264 and 282.

Particularly preferred pigment is: C.I. pigment violet 1,2,19,23,32,37 and 39.

Particularly preferred pigment is: the C.I. pigment Blue 15: 1,15:2,15:3,15:4,16,56,61 and (bridging) aluminium phthalocyanine pigment.

Particularly preferred pigment is: C.I. pigment orange 5,13,16,34,40,43,59,66,67,69,71 and 73.

Particularly preferred pigment is: C.I. pigment Green 7 and 36.

Particularly preferred pigment is: C.I. pigment brown 6 and 7.

Suitable pigment also comprises the mixed crystal of above-mentioned particularly preferred pigment.In mixed crystal (being also referred to as solid solution), usually but be not often, the molecule of each component enters into the identical lattice of one of component.The X-ray diffraction pattern of gained crystalline solid is represented the solid feature, and it can be clearly makes a distinction with the pattern of the physical mixture of the same composition of same ratio.In this physical mixture, can distinguish the X ray picture of each component, and the disappearance of many lines is to have formed one of standard of solid solution in these lines.Commercially available example is that it is the mixed crystal of C.I. pigment violet 19 and C.I. Pigment red 202 available from the pinkish red RT-355-D of the Cinquasia of CibaSpecialty Chemicals.Under given conditions, different quinacridone intermingling form solid solution.

For black ink, suitable paint material comprises blackout, for example: from Regal 400R, Mogul L, the Elftex 320 of Cabot Co. company; Perhaps from Carbon Black FW18, Special Black 250, Special Black 350, SpecialBlack 550, Printex 25, Printex 35, Printex 55, the Printex 150T of DEGUSSA Co. company; And C.I. Pigment black 7 and C.I. Pigment black 11.

For example, can obtain the neutral black jetted ink, for example as described in European patent application EP-A1593718 in a review by carbon black and green pigment, magenta pigment or cyan and magenta pigment are sneaked in the printing ink.

Ink-jet applications also needs one or more special looks (spot colours), for example is used to pack ink jet printing or textile ink-jet printing.Printing of ink-jet placard and point of sale are showed usually needs silver color and gold.Particularly preferred pigment is: C.I. pigment metal 1,2 and 3.The illustrative examples of mineral dye comprises: titanium dioxide, barium sulfate, lime carbonate, zinc oxide, lead sulfate, lead and yellow-collation, zinc yellow, red iron oxide (III), cadmium red, ultramarine, Prussian blue, chromoxide green, cobalt green, amber, titanium is black and synthetic iron black.Titanium dioxide is the preferred pigments that is used for white ink.

Pigment particles in the painted jetted ink should be enough little, crosses ink-jet printing apparatus to allow the printing ink free-flow, especially at the nozzle place.For maximum colour strength and slow down for the sedimentation, also need to use small-particle.

The mean particle size of the pigment in the painted jetted ink should be between 0.005 to 15 μ m.Average pigment granularity preferably between 0.005 to 5 μ m, more preferably between 0.005 to 1 μ m, is preferably between 0.005 to the 0.3 μ m, most preferably between 0.040 to 0.150 μ m especially.As long as can realize target of the present invention, then can use bigger pigment granularity.

But, be used to comprise for example TiO ₂The average pigment granularity of the white inkjet ink of pigment is preferably between 0.100 to 0.300 μ m.

Dispersion agent

The jetted ink of radiation-hardenable can further contain dispersion agent, to obtain stable pigment dispersion in jetted ink.

Paragraph [51] at unpub EP-A 06122098 (on October 11st, 2006 filed an application) discloses preferred dispersing agent in [87].

Dispersion synergists

The jetted ink of radiation-hardenable can further contain dispersion synergists.Dispersion synergists is used for improving the dust dispersion quality and the dispersion stabilization of jetted ink pigment dispersion.The mixture of dispersion synergists can be used for further improving dispersion stabilization.

Dispersion synergists is made of anionicsite and cationic moiety usually.The anionicsite of dispersion synergists demonstrates some molecular mimicry with coloured pigment usually; The cationic moiety of dispersion synergists is made of one or more protons and/or positively charged ion, with the electric charge of the anionicsite of offsetting dispersion synergists.

Curable magenta ink-jet ink according to the present invention preferably contains dispersion synergists.

Preferred dispersion synergists is disclosed among the unpub EP-A 05111356,05111357,05111358 and 05111360 (all submitting on November 28th, 2005).

Stopper

Radiation curable compositions can also contain stopper, and it is also referred to as stablizer.Suitable stopper comprises: phenol antioxidant, hindered amine as light stabilizer, fluor (phosphor) type antioxidant, Hydroquinone monomethylether, quinhydrones, tert-butyl catechol or pyrogallol.

Suitable commodity stopper for example is: Sumilizer GA-80, Sumilizer GM and Sumilizer GS that Sumitomo Chemical Co.Ltd. produces; Genorad 16, Genorad 18 and Genorad 20 available from Rahn AG; Irgastab UV10 and Irgastab UV22, Tinuvin 460 and CGS20 available from Ciba Specialty Chemicals; Floorstab UV series (UV-1, UV-2, UV-5 and UV-8) available from Kromachem Ltd; Additol S series (S100, S110, S120 and S130) available from Cytec Surface Specialties.

Because these stoppers of excessive interpolation can reduce the curing sensitivity of printing ink, therefore preferably before blend, determine to stop the polymeric amount.With respect to the gross weight of inkjet ink composition, the amount of stopper is preferably and is lower than 5 weight %, more preferably is lower than 2.5 weight %.

Tensio-active agent

Jetted ink can contain at least a tensio-active agent.Tensio-active agent can be negatively charged ion, positively charged ion, nonionic or zwitterionics, and the gross weight based on jetted ink adds with the total amount less than 20 weight % usually, and the gross weight based on jetted ink adds with the total amount less than 10 weight % especially.

Suitable tensio-active agent comprises: the sulfosuccinate ester salt of the ester salt of fluorizated tensio-active agent, soap, higher alcohols, alkylbenzene sulfonate, higher alcohols and phosphate ester salt are (for example, Sodium dodecylbenzene sulfonate and dioctyl sodium sulphosuccinate), ethylene oxide adduct, acetylenediol (acetylene glycol) and the ethylene oxide adduct thereof of the ethylene oxide adduct of the ethylene oxide adduct of higher alcohols, alkylphenol, polyhydric alcohol fatty acid ester (for example, polyoxyethylene nonylplenyl ether and available from AIR PRODUCTS﹠amp; The SURFYNOL104 of CHEMICALS INC., 104H, 440,465 and TG).

For non-aqueous ink-jet inks, preferred surfactants is selected from fluorine surfactant (for example fluorinated hydrocarbons) and silicone surfactant.Silicone is generally siloxanes and can is the siloxanes of oxyalkylated siloxanes, polyether-modified siloxanes, polyether-modified hydroxyl-functional, the siloxanes of amine modification, epoxide modified siloxanes and other modified form or their combination.Preferred siloxanes is polymkeric substance, for example polydimethylsiloxane.

In curable inkjet printing ink, fluorinated compound or silicone compounds can be used as tensio-active agent, preferably use crosslinkable tensio-active agent.Polymerisable monomer with surfactivity effect comprises the siloxanes of silicone modified acrylate, silicone modified methacrylic ester, acroleic acid esterification, polyether-modified acrylic acid modified siloxanes, fluorinated acrylic ester and fluorinated methyl acrylate.Polymerisable monomer with surfactivity effect can be simple function, two senses, trifunctional or higher functional (methyl) acrylate or their mixture.

The preparation of jetted ink

Curable inkjet printing ink can prepare by ground pigment in dispersion medium, preferably exists under the polymeric dispersant and carries out.

Mixing device can comprise: pressure kneader, open kneader, planetary-type mixer, dissolver and Dalton multimixer.Suitable grinding and diverting device are ball mill, ball mill (pearl mill), colloidal mill, high speed dispersion device, two roller, bead mill, paint mixing unit and three rollers.Also can use ultrasonic energy to prepare dispersion.

The material that can use number of different types is as grinding medium, for example: glass, pottery, metal and plastics.In preferred embodiment, grinding medium can contain particle, and preferred is spherical substantially, for example the bead that is made of macromolecule resin or the stable zirconium oxide bead of yttrium substantially.

In mixing, grinding and dispersive process, each process is carried out preventing heat accumulation under cooling, and carries out under the basic illumination condition of getting rid of actinic radiation as much as possible.

Curable pigment inkjet ink can contain more than a kind of pigment.Can use the independent dispersion of every kind of pigment to prepare jetted ink, perhaps alternatively, several pigment can be mixed when preparing dispersion and grind altogether.

Dispersion process can adopt continuously, intermittently or the semi-batch pattern carry out.

The preferred amount of each component of abrasive material (mill grind) and ratio are according to the purposes of concrete material and expection and wide region changes.The content of grinding mixture comprises abrasive material and grinding medium.Abrasive material contains pigment, polymeric dispersant and liquid vehicle.For jetted ink, remove grinding medium, pigment exists with 1 to 50 weight % in abrasive material usually.Pigment is 20: 1 to 1: 2 with respect to the weight ratio of polymeric dispersant.

But the milling time wide region changes and depends on pigment, selected mechanism and delay condition, initial granularity and required final size etc.In the present invention, can prepare the pigment dispersion of mean particle size less than 150nm.

After grinding is finished, adopt isolation technique commonly used that grinding medium is separated with the particulate product of having ground (doing dispersion form or liquid dispersion form), described isolation technique commonly used for example: filtration, sieve by screen cloth etc.Usually screen cloth is packed in the shredder (for example ball mill).The preferred condensed pigment that adopts filtration to have ground separates with grinding medium.

Usually expectation is made spissated abrasive material form with jetted ink, then it is diluted to suitable concentration and is used for ink-jet printing system.This technology allows from the relatively large coloring printing ink of device preparation.By dilution, jetted ink is adjusted to the required viscosity of concrete purposes, surface tension, color, tone, saturation density and printing zone coverage.

In the preparation of jetted ink, preferably carry out one or more degassing steps, from printing ink, to remove air or bubble.Preferably outgas by heating and/or decompression.Step can outgas on spissated pigment dispersion and/or final inkjet ink composition.

Printing device

Curable inkjet printing ink can be ejected into the printing ink small droplets on the printing ink reception surface through nozzle with controllable mode by one or more print heads and spray, and described printing ink receives the surface and moves with respect to print head.

The preferred print head that is used for ink-jet printing system is a piezoelectric heads.Piezoelectric ink jet printing is based on to piezoelectric ceramics transmodulator (transducer) the moving of piezoelectric ceramics transmodulator when applying voltage.Apply the shape that voltage changes the piezoelectric ceramics transmodulator on the print head, thereby produce the space, printing ink is filled in wherein.When removing voltage once more, pottery expand into its original shape, goes out an oil dripping China ink from print head ejects.But ink jet printing method according to the present invention is not limited to the piezoelectric ink jet printing.Can adopt other ink jet printing head, comprise all kinds, for example successive type and thermal control, Electrostatic Control and acoustic control drop on demand ink jet (drop on demand) type.

Under high print speed, printing ink must easily spray from print head, this physical property to printing ink has proposed a lot of restrictions, for example the low viscosity under the injection temperature (changing between 25-110 ℃), surface energy that print head nozzle can form essential small droplets, can be converted into the homogeneous liquid of dry printing zone etc. fast.

Ink jet printing head is crossed over the printing ink that moves usually and is received surface flyback in a lateral direction.Usually ink jet printing head does not print in returning the way.Preferred bidrectional printing is to obtain high area turnout (areal throughput).Another kind of preferred printing process is " one way printing process ", and it can use the page width ink jet print head or the multiple staggered ink jet printing head of the whole width that covers the printing ink receptor surface to carry out.In the one way printing process, it is static that ink jet printing head keeps usually, and transmit below ink jet printing head printing ink reception surface.

Solidification equipment

Radiation-hardenable composition (preferred radiation-hardenable jetted ink) can solidify by being exposed under the actinic radiation and/or passing through electrocuring.Preferably be cured by be exposed under the actinic radiation or comprehensively by comprehensive electrocuring.

Solidification equipment can be installed with the print head combination of ink-jet printer, moves thereupon, thereby promptly be exposed to curing radiation in the time that curable liquid is lacked very much after injection.

In this set, may be difficult to provide the enough little source of radiation that is connected on the print head and moves thereupon.Therefore, can use the source of radiation of stationary fixing, for example, the curing ultraviolet source that is connected with source of radiation by flexible radiation conduction device (for example fiber optics bundle or internal reflection metal hose).

Perhaps, can be by arranging a plurality of mirrors (comprising the mirror on the print head), and provide actinic radiation to print head from stationary source.

The source of radiation of being arranged to not move with print head can also be that the horizontal expansion leap treats that solidified printing ink receives surface and the elongation source of radiation adjacent with the transverse path of print head, thereby makes the image in a row that is formed by print head subsequently pass through the source of radiation below step by step or continuously.

The preferred UV source of source of radiation.Uv-radiation or UV-light are also referred to as UV radiation or UV light.As long as the light of emission part is absorbed by light trigger or photoinitiator system, can adopt any UV light source as source of radiation, for example high voltage mercury lamp or low pressure mercury lamp, cold-cathode tube, black light, ultraviolet LED, Ultra-Violet Laser or photoflash lamp.Wherein, preferred source of radiation is the source of radiation that demonstrates the UV-light of the relative long wavelength with 300-400nm predominant wavelength.Especially because the UV-A light source reduces scattering of light and can obtain more effective inside solidification, so preferably it.

As described below, the UV radiation is divided into UV-A, UV-B and UV-C usually:

UV-A:400nm to 320nm

UV-B:320nm to 290nm

UV-C:290nm to 100nm.

In addition, can be continuously or use the light source of two kinds of different wave lengths or brightness to solidify image simultaneously.For example, for example can select a UV source to make its radiation of sending be rich in UV-C, particularly the UV-C of 260nm-200nm.And the radiation that send in the 2nd UV source can be rich in UV-A, for example the lamp of doped gallium or the UV-A different lamp all high with UV-B.Found to use the advantage in two kinds of UV sources, for example curing speed is fast.

For promoting to solidify, ink-jet printer comprises one or more oxygen consumption unit usually.The oxygen consumption device is placed under nitrogen or other relative inertness gas (for example CO2) atmosphere, have adjustable position and adjustable inert gas concentration, in curing environment, to reduce the concentration of oxygen.Remaining oxygen level remains on usually and is low to moderate 200ppm, but is generally 200ppm-1200ppm.

Embodiment

Material

Except as otherwise noted, all material used among the embodiment is all easily originated available from standard, for example Aldrich Chemical Co. (Belgium) and Acros (Belgium).

DPGDA is the two functional acrylate's monomers that derive from CYTEC SURFACE SPECIALTIES.

Craynor CN386 is the amine modification acrylate synergistic agent from SARTOMER.

Darocur TPO is the I type light trigger from CIBA SPECIALTY CHEMICALS.

Genocure ITX is the II type light trigger from RAHN AG.

Genocure EPD is the amine synergistic agent from RAHN AG.

Genorad 16 is the stablizer from the UV-curing composition of RAHN AG.

PBlue15:4 is the green pigment Hostaperm BlueP-BFS from CLARIANT.

Solsperse 39000 is the hyper-dispersant from NOVEON.

Solsperse 5000 is the dispersion synergists from NOVEON.

Solsperse 35000 is the hyper-dispersant from NOVEON.

Byk UV3510 is the tensio-active agent from BYK CHEMIE GMBH.

BYK333 is the tensio-active agent from BYK CHEMIE GMBH.

SR9003 is SARTOMER 9003, is the ethoxylated neopentylglycol diacrylate from SARTOMER.

SFBlue 15:3 is the pigment Sunfast Blue 15:3 from SUN CHEMICALS CORPORATION.

BHT=2,6 di tert butyl 4 methyl phenol is the stopper from Aldrich.

Measuring method

Curing speed, viscosity, photic jaundice and adhesivity are used for estimating UV and solidify jetted ink.

Curing speed: with maximum output per-cent the measuring of lamp as curing speed or sensitivity.Numerical value is low more, and then curing speed is high more.When swiping, cannot see when damage, just think sample completely solidified with Q-drift (tip).

Viscosity: adopt the viscosity of Brookfield DV-H+ viscometer at 25 ℃ of measurement curable inkjet printing ink down and under the 3RPM shearing rate.

Photic jaundice: by measuring the b of composition coating ^*Value is come the photic jaundice effect of assess sample.Adopt rod to be coated with device and the 10 μ m excellent coating composition that winds the line.Make each coating curing on the Fusion DRSE-120 transport unit that is equipped with Fusion VPS/1600 lamp (D-bulb), described transport unit is uploaded feeding sample in travelling belt with the speed of 20m/min under the UV-lamp.On white PE paper, be coated with.In coating back 24 hours, measure the b of the aberration finger-length measurement of among CIE (Commission International de l ' Eclairage), stipulating with spectrophotometer (Gretag SPM50) ^*Value.In this case, at light source D50, light source spectral filter (light source filter) is not provided, with pure white as being to measure under 2 ° the condition with reference to white, visual angle.Research contains the jaundice effect of the composition of green pigment.Measure the b of cyan colored film ^*-value: b ^*-value is fewly more negative, and then the gained coating color is owing to the effect of light-initiated system becomes yellow more.

Adhesivity:, use Braive No.1536 cross cut test machine (deriving from BRAIVE INSTRUMENTS) and Tesatape according to international standard ISO2409:1992 (E) ^TMThe 4104PVC adhesive tape carries out cross cut test and estimates adhesivity, and otch is spaced apart 1mm, and the gross weight of using is the load of 600g.Estimate according to following classification:

The edge of 0=otch is smooth fully: none peels off (=excellent adhesivity) the grid square.

1=locates the small pieces disbonding in the intersection (intersection) of otch.Affected quadrature (cross-cut) area is not more than 5%.

The 2=coating is peeled off along the edge and/or at the infall of otch.Affected quadrature area is greater than 5%, but not significantly greater than 15%.

The 3=coating is partly or entirely peeled off with strip along notching edge, and/or on the grid top of different piece or all peel off.Affected quadrature area is significantly greater than 15%, but not significantly greater than 35%.

The 4=coating is peeled off with strip along notching edge, and/or on some grid tops or all break away from (detach).Affected cross-sectional area is significantly greater than 35%, but not significantly greater than 65%.

5=even employing rank 4 can not be carried out any degree of peeling off of fractionated.

Embodiment 1

Coinitiator COINI-01's to COINI-10 is synthetic

Prepare COINI-01 to COINI-10 according to scheme 1.

Scheme 1

In scheme 1, acrylic compound (1) is as michael acceptor.Provide in table 5 according to scheme 1 employed acrylic compound (1), secondary amine (2) and resulting coinitiator (3).

In the reactor of 125ml, in the presence of as the 0.22g BHT of stablizer, 0.15 mole of suitable acrylate (1) is heated to 80 ℃.Keep 80 ℃ temperature and added 0.30 mole of amine (2) through 1 hour.Continue this down at 80 ℃ and reacted other 5 hours, monitor this reaction mixture with gas-chromatography simultaneously.When finishing, reaction mixture is cooled to room temperature.Gained coinitiator (3) is enough pure, directly uses without being further purified.

Table 5

Coinitiator (3)	Acrylate derivative (1)	Secondary amine (2)
			COINI-01	MI-01	AM-01
COINI-02	MI-02	AM-01
			COINI-03	MI-02	AM-02
COINI-04	MI-02	AM-06
			COINI-05	MI-04	AM-01
COINI-06	MI-04	AM-02
			COINI-07	MI-05	AM-06
COINI-08	MI-05	AM-01
			COINI-09	MI-05	AM-02
COINI-10	MI-05	AM-03
			COINI-11	MI-05	AM-04

Coinitiator COINI-12's is synthetic

According to scheme 2 preparation coinitiator COINI-12.

Scheme 2

Under 50 ℃, with 1 of 10.1g (0.042 mole), two (the vinylsulfonyl)-2-hydroxy propanes (4) of 3-are dissolved in the 50ml 2-butanone.Keep 50 ℃ temperature, drip 8.6g (0.084 mole) N simultaneously, N, N '-trimethylammonium quadrol (5).At 50 ℃ reaction was continued 1 hour, monitor this reaction mixture with gas-chromatography simultaneously.When finishing, the vapourisation under reduced pressure solvent.Dry oily residue under vacuum.Confirm structure with gas chromatography-mass spectrum.

Coinitiator COINI-13's to COINI-15 is synthetic

Except using acetone to replace 2-butanone, use divinyl sulphones and the secondary amine shown in the table 6, according to preparing COINI-13 to COINI-15 about the described method of COINI-12 as the solvent.

Table 6

The divinyl sulfone derivatives is commercially available or can be according to synthetic method known in the art preparation.

Coinitiator COINI-27's is synthetic

According to scheme 3 preparation coinitiator COINI-27.

Scheme 3

In toluene (765ml) solution of morpholine (1) (200.4g, 2.3 moles) and 1-bromo-3-chloropropane (2) (393.6g, 2.5 moles), add aqueous sodium hydroxide solution (1N) (1035ml).With this mixture (two-phase) at 60 ℃ of heating and stir about 6 hours.

Reaction mixture is cooled to room temperature, the separation of methylbenzene phase, and use MgSO ₄Dry.Behind the evaporating solvent, residue is filtered to remove formed precipitation.Evaporated filtrate obtains 4-(3-chloropropyl) morpholine (3) of 332.6g colorless oil.

In ethanol (1000ml) solution of 4-(3-chloropropyl) morpholine (3) (327.3g, 2.0 moles), add propylamine (591.1g, 10.0 moles) in batches, simultaneously temperature is remained under 40 ℃.After being cooled to room temperature, add potassiumiodide (33.2g, 0.2 mole).Then reaction mixture is heated to and refluxes and stirred 20 hours.Reaction mixture is cooled to room temperature and filtration, to remove formed salt.Behind the evaporating solvent, residue is placed methyl-tertbutyl ether (1500ml) and stirred 2 hours.Remove by filter white depositions, and make it place distilled water (350ml) also pH to be transferred to 11.80 with aqueous sodium hydroxide solution (5N).This solution is extracted once with methyl-tertbutyl ether (400ml) extracting twice and with ethyl acetate (500ml).Through MgSO ₄Dry collected extract filters and concentrates, and obtains (3-morpholine-4-base-propyl group)-propyl group-amine (4) of 118.2g yellow oily.

With ethyl acetate (580ml) solution of pentaerythritol tetracrylate (5) (111.4g, 0.3162 mole) and 2,6 di tert butyl 4 methyl phenol (1.4g, 0.006324 mole) 80 ℃ of heating.

Adding (3-morpholine-4-base-propyl group)-propyl group-amine (4) under 80 ℃ (117.8g, 0.6323mol).With mixture stir about 18 hours.

Decompression removes down and desolvates, and obtains the COINI-27 of 221.5g yellow oily.

Coinitiator COINI-30's is synthetic

According to scheme 4 preparation coinitiator COINI-30.

Scheme 4

With ethyl acetate (750ml) solution of pentaerythritol tetracrylate (2) (158.6g, 0.45 mole) and 2,6 di tert butyl 4 methyl phenol (9.9g, 0.0045 mole) 45 ℃ of heating.

Under the situation of reacting by heating mixture not, drip N methyl piperazine (1) (90.1g, 0.90 mole).Reaction mixture 45 ℃ of following stir abouts 2 hours, and was at room temperature stirred 15 hours.

Decompression removes down and desolvates, and obtains the COINI-30 of 264.4g yellow oily.

Contrast coinitiator COMPCOINI-01's is synthetic

According to scheme 5 preparation contrast coinitiator COMPCOINI-01.

Scheme 5

With ethyl acetate (30ml) solution of pentaerythritol tetracrylate (2) (14.1g, 0.04 mole) and 2,6 di tert butyl 4 methyl phenol (0.09g, 0.0004 mole) 80 ℃ of heating.With morpholine (1) (7.0g, 0.08 mole) 80 ℃ of heating.With mixture stir about 18 hours.Decompression removes down and desolvates, and obtains the COMPCOINI-01 of 21.4g yellow oily.

Embodiment 2

The present embodiment explanation contains the high curing rate of the jetted ink of the present invention of I type light trigger.

The preparation of jetted ink INV-01 to INV-10 and COMP-01 to COMP-03

The preparation of spissated cyan dispersion

At first,, and use the Eiger ball mill to handle this mixture, prepare the spissated green pigment dispersion of forming shown in the table 7 by use dissolver hybrid pigment, dispersion agent, dispersion synergists and optional stablizer.

Table 7

Compound	Content (wt%)
		PBlue 15:4	20.0
Solsperse 39000	20.0
		Solsperse 5000	0.5
Genorad 16	1.0
		DPGDA	58.5

UV solidifies the preparation of jetted ink

The composition that UV solidifies jetted ink INV-01 to INV-10 and COMP-01 to COMP-03 is provided in the table 8.By under stirring at room, the ink component of table 8 joined in the spissated green pigment dispersion prepare printing ink.Weight percent (wt%) is that gross weight with radiation-hardenable composition is a benchmark.Each sample comprises the coinitiator (except that COMP-01) of equivalent (mole number with amine functional group is a benchmark).

Table 8

wt％：	COMP-01	COMP-02	COMP-03	INV-01	INV-02
						Craynor CN386	x	10.00	x	X	x
Genocure EPD	x	x	5.60	X	x
						COINI-01	x	x	x	13.50	x
COINI-02	x	x	x	X	11.60
						Darocur TPO	10.00	10.00	10.00	10.00	10.00
PBlue 15:4	3.00	3.00	3.00	3.00	3.00
						Solsperse 39000	3.00	3.00	3.00	3.00	3.00
Solsperse 5000	0.08	0.08	0.08	0.08	0.08
						Genorad 16	1.0	1.0	1.0	1.0	1.0
DPGDA	82.92	72.92	77.32	69.42	71.32
							INV-03	INV-04	INV-05	INV-06	INV-07
COINI-03	11.30	x	x	X	x
						COINI-04	x	10.50	x	X	x
COINI-05	x	x	8.50	X	x
						COINI-06	x	x	x	7.20	x
COINI-07	x	x	x	X	7.20
						Darocur TPO	10.00	10.00	10.00	10.00	10.00
PBlue 15:4	3.00	3.00	3.00	3.00	3.00
						Solsperse 39000	3.00	3.00	3.00	3.00	3.00
Solsperse 5000	0.08	0.08	0.08	0.08	0.08
						Genorad 16	1.00	1.00	1.00	1.00	1.00
DPGDA	71.62	72.42	74.42	75.72	75.72
							INV-08	INV-09	INV-10
COINI-08	7.20	x	x
						COINI-09	x	6.70	x
COINI-10	x	x	4.50
						Darocur TPO	10.00	10.00	10.00
PBlue 15:4	3.00	3.00	3.00
						Solsperse 39000	3.00	3.00	3.00
Solsperse 5000	0.08	0.08	0.08
						Genorad 16	1.00	1.00	1.00
DPGDA	75.72	76.22	78.42

Use rod to be coated with device and 10 μ m coiling rod, inkjet ink composition is coated on the do not have glue-line 100 μ m PET base materials of (unsubbed).On the Fusion DRSE-120 conveyer that is equipped with Fusion VPS/1600 lamp (D-bulb), solidify each coating, this conveyer under the UV lamp on travelling belt with the speed transportation sample of 20m/min.Measure curing speed.

The viscosity and the curing speed of jetted ink are summarised in the table 9.

Table 9

Sample	Viscosity under 25 ℃	Curing speed
			COMP-01	18.9	＞1,000
COMP-02	22.5	＞1,000
			COMP-03	19.1	200
INV-01	34.8	65
			INV-02	33.0	50
INV-03	38.4	50
			INV-04	37.6	50
INV-05	51.3	35
			INV-06	24.7	70
INV-07	24.4	70
			INV-08	25.8	50
INV-09	24.4	85
			INV-10	52.0	45

Clearly visible by table 9, the comparative ink (COMP-02 and COMP-03) that does not have the comparative ink (COMP-01) of coinitiator or have a typical commodity amine coinitiator has low curing speed, and all printing ink of the present invention (INV-01 to INV-10) that contain coinitiator of the present invention (COINI-1 to COINI-10) all have high curing rate.This shows that coinitiator COINI-01 to COINI-10 has improved the curing speed of the curable inkjet ink composite that contains I type light trigger, and does not undesirably increase the viscosity of jetted ink.

Embodiment 3

Embodiment 3 has illustrated the influence of coinitiator of the present invention to the curing speed of composition, and described composition comprises the combination of I type light trigger and II type light trigger.

Jetted ink composition with other dilutes above-mentioned spissated green pigment dispersion, obtains final jetted ink, and its composition is as shown in table 10.

The amount of coinitiator makes that the volumetric molar concentration of coinitiator is constant (mole number with amine functional group is a benchmark) in all ink samples.

Table 10

wt％：	COMP-4	COMP-5	COMP-6	INV-11	INV-12
						Craynor CN386	x	10.00	x	x	X
Genocure EPD	x	x	5.60	x	X
						COINI-01	x	x	x	13.50	x
COINI-02	x	x	x	x	11.60
						Darocur TPO	5.00	5.00	5.00	5.00	5.00
Genocure ITX	5.00	5.00	5.00	5.00	5.00
						PBlue15:4	3.00	3.00	3.00	3.00	3.00
Solsperse 39000	3.00	3.00	3.00	3.00	3.00
						Solsperse 5000	0.08	0.08	0.08	0.08	0.08
Genorad 16	1.00	1.00	1.00	1.00	1.00
						DPGDA	82.92	72.92	77.32	69.42	71.32
	INV-13	INV-14	INV-15	INV-16	INV-17
						COINI-03	11.30	x	x	x	x
COINI-04	x	10.50	x	x	x
						COINI-05	x	x	8.50	x	x
COINI-06	x	x	x	7.20	x
						COINI-07	x	x	x	x	7.20
Darocur TPO	5.00	5.00	5.00	5.00	5.00
						Genocure ITX	5.00	5.00	5.00	5.00	5.00
PBlue15:4	3.00	3.00	3.00	3.00	3.00
						Solsperse 39000	3.00	3.00	3.00	3.00	3.00
Solsperse 5000	0.08	0.08	0.08	0.08	0.08
						Genorad 16	1.00	1.00	1.00	1.00	1.00
DPGDA	71.62	72.42	74.42	75.72	75.72
							INV-18	INV-19	INV-20
COINI-08	7.20	x	x
						COINI-09	x	6.70	x
COINI-10	x	x	4.50
						Darocur TPO	5.00	5.00	5.00
Genocure ITX	5.00	5.00	5.00
						PBlue15:4	3.00	3.00	3.00
Solsperse 39000	3.00	3.00	3.00

Solsperse 5000	0.08	0.08	0.08
						Genorad 16	1.00	1.00	1.00
DPGDA	75.72	76.22	78.42

Use rod to be coated with device and 10 μ m coiling rod, inkjet ink composition is coated on the 100 μ m PET base materials that do not have glue-line.On the FusionDRSE-120 conveyer that is equipped with Fusion VPS/1600 lamp (D-bulb), solidify each coating, this conveyer under the UV lamp on travelling belt with the speed transportation sample of 20m/min.Measure curing speed.

Table 11 has shown the viscosity and the curing speed of jetted ink.

Table 11

Sample	Viscosity under 25 ℃	Curing speed
			COMP-04	17.5	400
COMP-05	19.4	40
			COMP-06	16.8	45
INV-11	31.6	45
			INV-12	28.8	35
INV-13	35.0	45
			INV-14	35.4	35
INV-15	69.6	35
			INV-16	49.7	35
INV-17	25.3	35
			INV-18	24.0	35
INV-19	24.8	35
			INV-20	70.0	35

This embodiment clearly illustrates that, for the inkjet ink composition that contains the combination of I type (Darocur TPO) and II type (Genocure ITX) light trigger, coinitiator COINI-01 to COINI-10 is effective equally with well-known amine synergistic agent Craynor CN386 and Genocure EPD, some in addition better a little, but undesirably do not increase the viscosity of jetted ink.

Embodiment 4

Embodiment 4 explanations jetted ink according to the present invention is characterised in that: the amount of solidifying the back extractable content is low.

Use rod to be coated with device and 10 μ m coiling rod, the inkjet ink composition of table 12 is coated on the 100 μ m PET base materials that do not have glue-line.The Fusion DRSE-120 conveyer that use is equipped with Fusion VPS/1600 lamp (D-bulb) solidifies each coating, this conveyer under the UV lamp on travelling belt with the speed of 20m/min transportation sample.

Table 12

wt.％：	INV-21	INV-22	INV-23	INV-24
					SR9003	40.00	40.00	40.00	40.00
DPGDA	43.97	35.69	35.69	35.69
					Genocure ITX	5.00	5.00	5.00	5.00
Darocure TPO	-	5.00	5.00	5.00
					PBlue 15:4	-	3.00	3.00	3.00
SFBlue 15:3	2.00	-	-	-
					Solsperse 39000	2.00	3.00	3.00	3.00
Solsperse 5000	0.50	0.08	0.08	0.08
					BYK333	0.03	0.03	0.03	0.03
Genorad 16	1.00	1.0	1.0	1.0
					COINI-05	5.5	-	-	-
COINI-08	-	7.2	-	-
					COINI-10	-	-	7.2	-
COINI-11	-	-	-	7.2

Explore several methods and measured the amount of extractable content (extractable).Adopt the HPLC method, for example be suitable for measuring the method for Genocure EPD,, fail to determine extractable content as described in the unpub EP-A 06124637 (submission on November 23rd, 2006) as extractable content.Coinitiator proof of the present invention is difficult to concentration quantitative, and when they kept extracting in coating, concentration can be expected.With the contrast coinitiator for example Genocure EPD compare, the irreversible adsorption that reference compound carries out with low relatively concentration on the pillar of different liquid chromatography technologies (HPLC, GPEC, few hole dimension exclusion (oligopore sizeexclusion)) causes the analysis of extractable content very difficult.A kind of method based on gas-chromatography proves unique can carry out quantitative technology to the residue extractable content according to coinitiator of the present invention under enough sensitivity, can use in food uses with identity basis coinitiator of the present invention.In addition, adopt following method, fail to measure extractable content.

The sample of cut-off footpath 30mm from the solidified sample is with the extraction of 2.0ml acetonitrile.20mg reference compound (coinitiator) is dissolved in the 1.0ml acetonitrile, and then with 100 times of each diluted samples, preparation is with reference to sample.With 1 μ l inject GC (EPC of HP6890GC-system) with reference to sample and extract, (30m * 25mm df.0.25 μ m is by J﹠amp to use the BD1 post; W (nr.122-1023) supply), slowly rises to 325 ℃ from 100 ℃, and kept 325 ℃ of oven temperatures 5 minutes with the speed of 15 ℃/min.Use splitting ratio (split radio) is shunting/no split stream injector of 50/1 under 260 ℃.Use fid detector down at 300 ℃.Use helium as carrier gas, its flow velocity is 2ml/min.When not having extract, more than detectability, just can detect any coinitiator.This clearly illustrates that curable compositions of the present invention is applicable to food adaptability formulation (foodcompliant formulations).

Embodiment 5

The photic jaundice and the adhesivity of embodiment 5 explanations improvement jetted ink of the present invention.

The preparation of jetted ink INV-25 to INV-27 and COMP-07

The preparation of spissated cyan dispersion

At first,, and use NETZCH LMZ10 ball mill to handle this mixture, prepare the spissated green pigment dispersion that its composition is shown in Table 13 by use dissolver hybrid pigment, dispersion agent and stablizer in as the DPGDA that disperses media.

Table 13

Compound	Content (wt%)
		PBlue15:4	20.0
Solsperse 35000	20.0
		Genorad 16	1.0
DPGDA	59.0

UV solidifies the preparation of jetted ink

The composition that UV solidifies jetted ink UV-25 to INV-26 and COMP-07 and COMP-08 is provided in the table 14.By under stirring at room, the ink composition of table 14 joined in the spissated green pigment dispersion prepare printing ink.Weight percent (wt%) is that gross weight with radiation-hardenable composition is a benchmark.Each sample comprises the coinitiator of equivalent (mole number with amine functional group is a benchmark).

Table 14

wt.％：	COMP-07	INV-25	INV-26	COMP-08
					Genocure EPD	5.00	x	x	x
COINI-27	x	7.90	x	x
					COINI-30	x	x	6.00	x
COMPCOINI-01	x	x	x	11.50
					Darocur TPO	5.00	5.00	5.00	5.00
Genocure ITX	5.00	5.00	5.00	5.00
					PBlue15:4	3.00	3.00	3.00	3.00
Solsperse 35000	3.00	3.00	3.00	3.00
					Genorad 16	1.00	1.00	1.00	1.00
Byk UV3510	0.10	0.10	0.10	0.10
					DPGDA	77.90	75.00	76.90	71.40

Use rod to be coated with device and 10 μ m coiling rod, coating inkjet ink composition.On the Fusion DRSE-120 conveyer that is equipped with Fusion VPS/1600 lamp (D-bulb), solidify each coating, this conveyer under the UV lamp on travelling belt with the speed transportation sample of 20m/min.For evaluate cure speed, be not coated with on the 100 μ m PET base materials of glue-line having.

In order to estimate photic jaundice, on white PE paper, be coated with, measure the b of coating after 24 hours in coating ^*-value.In order to estimate adhesivity, use two kinds of dissimilar polypropylene bases.

The curing speed of jetted ink and photic jaundice are as shown in Table 15.

Table 15

Sample	Curing speed	b ＊Value
			COMP-07	45	-45.5
INV-25	40	-51.5
			INV-26	40	-51.5
COMP-08	40	-50.0

Compare the b of cyan colored film in the situation of Comparative composition COMP-07 with INV-26 with sample INV-25 of the present invention ^*Value is the more yellow (b that obviously becomes ^*Still less negative).

The results are shown in the table 16 of adhesiveness test.

Table 16

The nomenclature of polypropylene base is as follows:

The PP1=polypropylene base, its for French PR IPLAK preparation, available from the Priplak of Belgian ANTALIS ^TMClassic

PP2=is from the BuplexPP 3mm of B ü hrmannUbbens BV (Holland)

Comparative sample COMP-07 shows strong photic jaundice (table 15) and very poor (table 16) of adhesivity on polypropylene base.Both all produce improvement to photic jaundice (table 15) and adhesivity (table 16) for sample INV-25 of the present invention and INV-26, even its curing speed is slightly higher than COMP-07.COMP-08 compares with COMP-07, only adhesivity is had small improvement.

Claims (25)

1. radiation-hardenable composition, it comprises curable compound, light trigger and coinitiator, it is characterized in that, and described coinitiator represented by formula I,

Formula I

Wherein, MA is the residue of single functionality or low functionality michael acceptor;

L is a divalent linking group, and it is positioned two kinds of tertiary amines for the 1-3 position to the 1-10 position, and condition is that two kinds of amine are aliphatic amine;

R1, R2 and R3 represent the optional alkyl that replaces, the optional thiazolinyl that replaces, the optional alkynyl that replaces or optional (mixing) alkaryl that replaces independently;

Any two the essential atoms that can represent to form ring among R1, R2 and the R3;

Any two the essential atoms that can represent to form ring among R1, R2 and the R3 with the arbitrary atom of linking group L;

N is the integer of 1-6.

2. radiation-hardenable composition according to claim 1, wherein, MA is the residue that is selected from following single functionality or low functionality michael acceptor: (methyl) acrylate, (methyl) acrylamide, vinyl sulphone, vinylphosphonate, vinyl sulfonic acid ester, vinyl sulphonamide, maleimide, vinyl nitrile, vinyl ketone, vinyl aldehyde and vinyl sulfoxide.

3. according to each described radiation-hardenable composition of aforementioned claim, wherein, MA is the residue of two functionality or low functionality michael acceptor.

4. according to each described radiation-hardenable composition of aforementioned claim, wherein, residue MA does not contain polymerizable groups.

5. according to each described radiation-hardenable composition of aforementioned claim, wherein, residue MA contains polymerizable groups.

6. radiation-hardenable composition according to claim 5, wherein, described polymerizable groups is acrylate-based.

7. according to claim 5 or 6 described radiation-hardenable compositions, wherein, described coinitiator comprises the piperazine of morpholine part.

8. according to each described radiation-hardenable composition of aforementioned claim, wherein, the described divalent linker L among the formula I is C2 to a C6 aliphatic series divalent linker.

9. according to each described radiation-hardenable composition of aforementioned claim, wherein, the R1 among the formula I, R2 and R3 represent C1 to C5 alkyl.

10. according to each described radiation-hardenable composition of aforementioned claim, wherein, the described coinitiator of being represented by formula I is the reaction product of single functionality or low functionality michael acceptor and secondary amine, and described amine contains at least a other aliphatic tertiary amine.

11. radiation-hardenable composition according to claim 10, wherein, described secondary amine represented by formula II,

Formula II

Wherein, L ' is a divalent linker, and it is positioned secondary amine and tertiary amine for the 1-3 position to the 1-10 position, and condition is that two kinds of amine are aliphatic amine;

R4, R5 and R6 represent the optional alkyl that replaces, the optional thiazolinyl that replaces, the optional alkynyl that replaces or optional (mixing) alkaryl that replaces independently;

Any two the essential atoms that can represent to form ring among R4, R5 and the R6;

Any two the essential atoms that can represent to form ring among R4, R5 and the R6 with the arbitrary atom of linking group L '.

12. according to each described radiation-hardenable composition of aforementioned claim, wherein, described composition contains the mixture of at least two kinds of different coinitiators.

13. according to each described radiation-hardenable composition of aforementioned claim, wherein, described composition comprises Aminobenzoate type coinitiator.

14. according to each described radiation-hardenable composition of aforementioned claim, wherein, described curable compound is the vinyl ether acrylate.

15. according to each described radiation-hardenable composition of aforementioned claim, wherein, described light trigger is an I type light trigger.

16. radiation-hardenable composition according to claim 15, wherein, described I type light trigger is acylphosphine oxide or diacyl phosphine oxide.

17. according to each described radiation-hardenable composition of aforementioned claim, wherein, described radiation-hardenable composition comprises II type light trigger.

18. according to each described radiation-hardenable composition of aforementioned claim, wherein, described composition is a coating composition.

19. radiation-hardenable composition according to claim 18, wherein, described coating composition is as varnish, priming paint, jaqan or image recording layer.

20. according to each described radiation-hardenable composition among the claim 1-17, wherein, described composition is printing-ink or fluid.

21. radiation-hardenable composition according to claim 20, wherein, described composition is the jetted ink or the fluid of radiation-hardenable.

22. radiation-hardenable composition according to claim 21, wherein, described composition is that UV solidifies jetted ink or fluid.

23. according to the coinitiator of formula III,

Formula III

Wherein, R7, R8 and R9 represent the optional alkyl that replaces, the optional thiazolinyl that replaces, the optional alkynyl that replaces or optional (mixing) alkaryl that replaces independently;

R10 is hydrogen or methyl;

X represents-SO ₂-or-C (O)-O-;

L " expression C2 to C6 aliphatic series divalent linker;

A represents two functionality or polyfunctionality linking group, and its maximum functionality is 6;

M is selected from hydroxyl or (methyl) is acrylate-based;

N is the integer of 2-6;

M is the integer of 0-4, and condition is that n+m is not more than 6.

24. coinitiator according to claim 23, wherein, this coinitiator represented by formula IV,

Formula IV

Wherein, R7, R8, R9, R10, L ", A, M, n and m have with formula III in identical implication.

25. coinitiator according to claim 24, wherein, this coinitiator represented by formula V,

Formula V

Wherein, R7, R8, R9, L ", A and n have with formula III in identical implication.