CN100361815C - Liquid ink and recording apparatus - Google Patents

Abstract

There is disclosed a liquid ink comprising a photo acid generating agent that generates an acid upon irradiation with light, a coloring component, and at least one kind of a solvent that is polymerized in the presence of an acid. It is preferable that the amount of the photo acid generating agent contained in the liquid ink falls within a range of between 1 part by weight and 10 parts by weight relative to 100 parts by weight of the solvent, the coloring component consists of a pigment, and the solvent contains at least 50 parts by weight of an acid polymerizable compound, the acid polymerizing compound polymerizing in the presence of the acid, having an alicyclic skeleton and/or an aliphatic skeleton having a viscosity of 50 mPa.s or less and a boiling point of 150 DEG C or more under room temperature and atmospheric pressure.

Description

Ink jet recording device

The application is that application number is 03122927.1, and the applying date is on April 24th, 2003, and denomination of invention is divided an application for the application for a patent for invention of " liquid ink and recording equipment ".

Technical field

The present invention relates to the ink jet printing field, specifically, the present invention relates to a kind of ink jet recording device that uses liquid ink on recording medium, to form the printing ink image.

Background technology

Use the printing press of galley to be used to make the printed matter that needs a large amount of folders, as advertisement, the data of in enterprise, distributing or placard significantly.In recent years, used a kind of desired printing press (it can satisfy multiple needs and conservation) to substitute conventional printing press.Can at full speed obtain high quality printing, use the electrostatographic printing machine device of toner or liquid toner or ink-jet printer to be considered to provide gratifying required printing press.

This field is known, and as the printing press of the use galley of routine, the solvent system that contains pigment and organic solvent or solvent system liquid toner is used to desired printing press.Yet in this technology, organic solvent can be with very important amount evaporation when printing image in a large number.Consequently, the organic solvent that atmosphere on every side will be evaporated pollutes, and just is necessary to install exhaust apparatus or solvent recovery unit.

By the way, in ink-jet printer, before being directed onto on the printing paper surface, use by printing ink the printing ink of solvent system in airtight system, to operate.Consequently, the suitable exhaust measure of employing can solve the pollution problem to ambient atmosphere to a certain extent.Yet the printing ink that is used in the ink-jet printer is different from the printing ink that uses in the printing press that uses galley.Specifically, be necessary to make the printing ink that uses in the ink-jet printer to have the necessary flowability of ink jet.Therefore, in above-mentioned technology, the content of solvent should be quite high in the printing ink, and this pollution problem that will make the ambient atmosphere that solution causes because of organic solvent evaporation is difficulty very.

Need should be mentioned that also when using solvent system printing ink, the print surface of printing paper etc. can have a strong impact on the quality of printing image.For example, have the print surface of infiltration trend that the printing image is thickened, and printing image is relatively more difficult on impermeable print surface.In addition, the ink lay that forms at print surface needs the considerable time could drying.Therefore, when on bigger print surface, forming thicker image, because the mobile image of printing ink might be out of shape.In addition, state in the use in the technology of solvent, print surface has the possibility of damage when ink lay is dry.Therefore will obtain high-quality printed matter with this technology is not easy to.

Attracted people's attention as the photosensitive ink that can effectively overcome the problems referred to above and print system.In this technology, the photosensitive ink that is ejected on the print surface is penetrated by illumination, obtains the quick light slaking (being meant the drying that does not produce emission) of printing ink.The photosensitive ink that uses in this technology contains the polymerisable monomer of free radical, Photoepolymerizationinitiater initiater and pigment usually.

According to above-mentioned technology, might make ink lay behind light irradiation, no longer have flowability, can obtain the printed matter of better quality thus.Yet the printing ink that uses in this technology contains a large amount of carcinogens, generates agent as free radical.In addition, the volatility acrylic acid derivative that is used as the free radical polymerisable monomer has intense stimulus to skin, and tanginess.Naturally just need very careful during treatment of printing ink.In addition, the existence meeting of oxygen obviously suppresses radical polymerization in the air.And contained pigment can absorb the light of irradiation ink lay in the printing ink, consequently, does not just have the light of q.s in the ink lay depths.In this case, but conventional radical polymerization printing ink is just lower to the sensitiveness of light, therefore, for obtaining high-quality printed matter by this technology, just needs very big exposure system.

But once planned printing ink with light-cationic curing as printing ink, it is subjected in the air influence of oxygen less.Yet such conventional photosensitive ink contains can cause the solvent that is discharged into problem in the environment.In addition, this printing ink can solidify with comparalive ease automatically, becomes insoluble, will bring the additional problem of blocking inkjet nozzle.It is reported to also have the another kind of photosensitive composition that can be used to be coated with the cationic polymerization type of CD-ROM, it can spray in ink-jet system.In fact, can contain vinethene and bisphenol A type epoxy resin by the photosensitive composition of ink-jet systems eject as main component, these materials are considered to cause cancer.It still is insoluble serious problems that photosensitive composition is discharged in the environment.A kind of printing ink that contains cationic polymerization monomer (specific compositing monomer ratio is arranged) that is used for ink-jet was also proposed.This printing ink that is used for ink-jet also contains the very high-volatile specific vinethene compound of having of a kind of essential composition, and this has just caused above-mentioned similar problem.Simultaneously, when conventional vinethene compound and pigment use together, can cause the problem of this compound polymerizing power variation.

This field is also known with a kind of solid ink and is replaced aforesaid liquid printing ink to use for ink-jet.In this technology, the printing ink that at room temperature is solid is ejected on the print surface of printing paper after heat fused.In other words, this technology has formed a kind of system without solvent basically, has solved environmental problem thus.Also disclosed an embodiment simultaneously, the solid ink that this ink-jet is used is endowed light sensitivity, so that the ink lay that forms behind the ink jet is fixed.Yet, when using common pigment as colouring component to disperse, liquid lock takes place probably.Simultaneously, be difficult to make pigment to be dispersed in the printing ink.Therefore, in this technology, pigment is disperseed and stabilisation aspect the very big problem of existence.Therefore, be necessary to use a kind of pigment of special microcapsule type of costliness, perhaps, under regular situation, colouring component only limits to the dyestuff that can fade in time.

On the other hand; in the original ink-jet system that makes up, ink droplet is directly injected on the paper as printed medium, so that form ink lay on paper; the printing image that ink lay forms can blur usually, and perhaps the sense coloured light sensitiveness of printing image can change along with printed medium.In order to overcome these shortcomings, people have proposed a kind of ink jet recording device, wherein, photosensitive ink by disposable jet to first printed medium, use up the surface of slight cured printing ink layer then, ink lay is lost flowability, and the ink lay that will slightly solidify is transferred on the paper bulletin thing as second printed medium subsequently.Yet, at printing machine be used for the printing ink of this system, need carry out trickle control, to obtain being fit to transfer to the ink lay that partly solidifies on second printed medium to the amount and the radiation environment of light irradiation.In addition, optimum exposure can be according to color and difference.Therefore, above-mentioned ink jet recording device not too is suitable for the printing color image.

Should be noted also that it specifically is when print surface is a kind of absorbing medium,, therefore can produce a series of problems in the absorbability paper because conventional acrylic acid photo-curing ink-jet printing ink is difficult to be cured.

By the way, the jetted ink of conventional cation photocuring, its viscosity can automatically acutely change.In a single day this problem is because printing ink is rotten in time, and has produced acid in printing ink, this printing ink just can't deactivate, to such an extent as to produce many dark reactions in printing ink.This problem is very serious, because if the viscosity-modifying of jetted ink the problem as ink jet shape instability, printing repeatability difference will take place, and under even worse situation, ink jet is understood variation, and the situation of clogged with ink nozzle and so on can take place again.

Summary of the invention

The purpose of this invention is to provide a kind of ink jet recording device that can obtain printed matter with liquid ink.

On the one hand, the invention provides a kind of ink jet recording device that uses liquid ink to form the printing ink image on recording medium, described equipment comprises:

Shift the transfering part of recording medium;

Be contained in the inkjet type record head of described transfering part top, described inkjet type record head is injected in liquid ink on the recording medium, forms ink lay on recording medium;

The heating element heater of heating ink lay;

Wherein, described ink jet recording device also comprises the light source with light irradiation ink lay.

One preferred embodiment in, described heating element heater is the heater that separates installation with light source.

Another preferred embodiment in, described ink jet recording device also comprises gaseous matter through the gaseous material passage of light source, to obtain the gaseous material through heat exchange, light source and the set of gaseous state substance channel form heating element heater.

Another preferred embodiment in, described equipment also comprises the heating mantles that is connected with light source, injected the gaseous material after heat exchange in this heating mantles, and this heating mantles has recording medium, described recording medium comprises the ink lay behind the light irradiation of transferring on it.

Another preferred embodiment in, described light source is at the radiative infrared ray of launching simultaneously, described equipment also comprises the reflecting plate of reflected infrared ray and/or transmits ultrared transmission window, comprises light source and reflecting plate and/or transmits the heating element heater of window.

Another preferred embodiment in, described equipment also comprises the container that holds recording medium behind a plurality of smooth irradiation, heats with heating element heater in this container.

Another preferred embodiment in, described light source is launched light under the frequency electromagnetic waves effect;

Described equipment also comprises to light source provides the high frequency generating apparatus of frequency electromagnetic waves, the electromagnetic shield of ambient light source periphery, at least be formed with a hole on its surface facing to transfering part, be arranged in the heat production medium on the transfering part back side, it produces heat under the irradiation of frequency electromagnetic waves;

Heating element heater comprises launches light and electromagnetic light source, high-frequency electromagnetic wave generating device and heat production medium simultaneously.

Another preferred embodiment in, be arranged with a plurality of inkjet type record heads (4a, 4b, 4c, 4d), they spray the multiple inks that color differs from one another, and form the ink lay of different colours, carry out light irradiation and/or heating after forming a single ink lay each time.

On the other hand, the invention provides a kind of ink jet recording device that uses liquid ink to form the printing ink image on recording medium, described equipment comprises:

Shift the transfering part of recording medium;

The image carrier that contacts with described transfering part rotation;

The inkjet type record head, described inkjet type record head is injected in liquid ink on the image carrier, forms ink lay on image carrier;

The heating element heater of heating ink lay;

Wherein, described ink jet recording device also comprises the light source with light irradiation ink lay, and utilizes pressure or utilize pressure and heat, and the ink lay after the heating is transferred on the recording medium from image carrier.

Other purpose and advantage of the present invention is described below, and its part is not difficult clear by description, perhaps can be to understand by the practice of the present invention.By equipment and the combination that hereinafter particularly points out, can realize and obtain objects and advantages of the present invention.

Description of drawings

Here appended and as the accompanying drawing of this specification part, set forth embodiments more of the present invention, they and top general description and following to detailed description of the preferred embodiments together, explained principle of the present invention.

Fig. 1 illustrates to show the structure of one embodiment of the invention ink jet recording device;

Fig. 2 illustrates to show the structure of another embodiment of the present invention ink jet recording device;

Fig. 3 illustrates to show the structure of another embodiment of the present invention ink jet recording device;

Fig. 4 illustrates to show the structure of another embodiment of the present invention ink jet recording device;

Fig. 5 illustrates to show the structure in source;

Fig. 6 illustrates to show the structure of another embodiment of the present invention ink jet recording device;

Fig. 7 illustrates to show the structure of another embodiment of the present invention ink jet recording device;

Fig. 8 illustrates to show the structure of another embodiment of the present invention ink jet recording device;

Fig. 9 illustrates to show the structure of another embodiment of the present invention ink jet recording device;

Figure 10 illustrates to show the structure of another embodiment of the present invention ink jet recording device;

Figure 11 illustrates to show the structure of another embodiment of the present invention ink jet recording device; And

Figure 12 shows the relation of compd E p11 content and viscosity.

The specific embodiment

Now embodiment of the present invention will be described in conjunction with the accompanying drawings.In these figure, the part that is shown with identical or similar functions with same digital watch is repeated in this description avoiding.

The liquid ink of one embodiment of the invention is included under the light irradiation can acidic photic acid producing agent; Colouring component; And at least a solvent that can polymerization when having acid to exist.In other words, a kind of chemistry of the liquid ink of one embodiment of the invention representative amplifies the photosensitive composition of type.By the way, term used herein " liquid ink " is meant at room temperature mobile printing ink.Specifically, liquid ink is meant that viscosity is 50cp or littler in the time of 25 ℃, better is 30cp or littler printing ink.

If liquid ink of the present invention is penetrated by illumination, photic acid producing agent will produce acid.The catalyst action that makes polymerizable compound generation cross-linking reaction is just played in the acid of this generation.Simultaneously, the acid of generation can diffusion in ink lay.In addition, by heating, the cross-linking reaction that can promote the diffusion of acid and carry out when existing as the acid of catalyst.Different with radical polymerization, cross-linking reaction can not be subjected to the inhibition of oxygen.Therefore, single photon can cause a large amount of cross-linking reactions, thereby realizes high photosensitivity.In addition, even if in ink lay depths and absorbability printed medium inside, cross-linking reaction is carried out rapidly.Consequently, compare with radical polymerization, the ink lay of gained has obviously higher tack.

In this case,, use up the ink lay that irradiation and heating form the print surface ink jet, can make ink lay be unlikely mobile if use the liquid printing ink of this embodiment of the present invention.In other words, might obtain high-quality printing material, and used exposure system needn't be very big.By the way, need ink lay unlikely mobile to show thermoplasticity (flowability again when promptly being heated), although flowability can keep very short time again.

Also it is pointed out that different with the liquid ink that uses radical polymerization, the liquid ink of this embodiment of the present invention do not use may be carcinogenic free radical generate agent or chafe and the free radical polymerisable monomer of strong smell arranged.Therefore, can operate easily as the liquid ink of the present invention of this embodiment of the present invention.

In addition, in the liquid ink of this embodiment of the present invention, above-mentioned polymerisable compound is used as the part of solvent at least.Basically whole solvent is the theobromine polymerizable compound normally, i.e. polymerisable compound under sour existence condition.Therefore, if the ratio of this polymerizable compound and whole solvent is enough high, the evaporation capacity of organic solvent is just very little in print steps.Therefore, might solve, therefore need not to use exhaust apparatus or solvent recovery unit because of organic solvent evaporation causes the ambient atmosphere pollution problems.

Should be noted also that in one embodiment of the invention, needn't be with an organic solvent, and ink lay can solidify rapidly and do not flow.Therefore, image can easily be fixed on the print surface of various characteristics, can prevent image blurring simultaneously.In addition, print surface can not be dry destroyed because of ink lay.What also need to carry is, is contained in the liquid ink of one embodiment of the invention with high concentration as the pigment of colouring component, thereby can obtains clear and the outstanding printed patterns of weatherability is arranged.

Each composition of one embodiment of the invention liquid ink will be described below.

As mentioned above, the liquid ink of one embodiment of the invention is included in acidic photic acid producing agent under the light irradiation.Photic acid producing agent for example comprises, salt, diazol, quinonediazide compound, organohalogen compound, armaticity sulfonate compound, two sulphones, sulfonyl compound, sulfonate compound, sulfonium compound, sulphamide compound, iodine  compound, sulphonyl diazomethane compound and their mixture.

The object lesson of above-claimed cpd for example comprises, triphenylsulfonium triflate, diphenyl iodine  triflate, 2,3,4,4-tetrahydrochysene benzophenone-4-naphthoquinones two nitrine sulfonate, 4-N-anilino--2-methoxyphenyl diazo sulfonate, 4-N-anilino--2-methoxyphenyl diazo is right-phenethyl sulfate, 4-N-anilino--2-methoxyphenyl diazo-2-naphthyl sulfate, 4-N-anilino--2-methoxyphenyl diazo phenyl sulfate, 2,, 5-dimethoxy-4 '-N-4 '-methoxyphenyl carbonyl phenyl diazo-3-carboxyl-4-hydroxyphenyl sulfate, 2-methoxyl group-4-N-phenyl diazo-3-carboxyl-4-hydroxyphenyl sulfate, diphenyl sulphonyl methane, diphenyl sulphonyl diazomethane, diphenyl two sulfones, Alpha-Methyl styrax toluene fulfonate, pyrogallol three mesylates, the styrax toluene fulfonate, the MPI-103 (CAS 87709-41-9 number) that Midori Kagaku company makes, the BDS-105 (CAS. 145612-66-4 number) that Midori Kagaku company makes, the NDS-103 (CAS. 110098-97-0 number) that Midori Kagaku company makes, the MDS-203 (CAS. 127855-15-5 number) that Midori Kagaku company makes, the pyrogallol trimethylbenzene sulfonate (CAS. 20032-64-8 number) that Midori Kagaku company makes, the DTS-102 (CAS. 75482-18-7 number) that MidoriKagaku company makes, the DTS-103 (CAS. 71449-78-0 number) that Midori Kagaku company makes, the MDS-103 (CAS. 127279-74-7 number) that Midori Kagaku company makes, the MDS-105 (CAS. 116808-67-4 number) that Midori Kagaku company makes, the MDS-205 (CAS.81416-37-7 number) that Midori Kagaku company makes, the MBS-105 (CAS.149934-68-9 number) that Midori Kagaku company makes, the TMS-105 (CAS. 127820-38-6 number) that Midori Kagaku company makes, the NB-101 (CAS. 20444-09-1 number) that Midori Kagaku company makes, the NB-201 (CAS. 4450-68-4 number) that MidoriKagaku company makes, the DNB-101 (CAS. 114719-51-6 number) that Midori Kagaku company makes, the DNB-102 (CAS. 131509-55-2 number) that Midori Kagaku company makes, the DNB-103 (CAS. 132898-35-2 number) that Midori Kagaku company makes, the DNB-104 (CAS. 132898-36-3 number) that Midori Kagaku company makes, the DNB-105 (CAS. 132898-37-4 number) that Midori Kagaku company makes, the DAM-101 (CAS. 1886-74-4 number) that Midori Kagaku company makes, the DAM-102 (CAS. 28343-24-0 number) that Midori Kagaku company makes, the DAM-103 (CAS. 14159-45-6 number) that MidoriKagaku company makes, the DAM-104 that Midori Kagaku company makes (CAS. 130290-80-1 number and CAS. 130290-82-3 number), the DAM-201 (CAS. 28322-50-1 number) that Midori Kagaku company makes, the CMS-105 that Midori Kagaku company makes, the DAM-301 (CAS.138529-81-4 number) that MidoriKagaku company makes, the SI-105 (CAS.34694-40-7 number) that Midori Kagaku company makes, the NDI-105 (CAS. 133710-62-0 number) that Midori Kagaku company makes, the UVACURE 1591 that the EPI-105 (CAS. 135133-12-9 number) that Midori Kagaku company makes and Dicel UCB. S.A. (BE) Bruxelles Belgium make.

Can use compound that following formula provides as photic acid producing agent:

[C ₆H ₅Fe ⁺C ₆H ₅]PF ₆ ^-

[C ₆H ₅Fe ⁺C ₆H ₅]PF ₆ ^-

In the superincumbent general formula, C1 and C2 represent to form the carbon atom of singly-bound or two keys respectively, and R10 represents hydrogen atom, fluorine atom, alkyl or aryl, and R11 and R12 represent the unit price organic group respectively.R11 and R12 might be interconnected to form circulus.

Can also use compound that following formula provides as photic acid producing agent:

In the superincumbent general formula, Z represents alkyl.

Especially, need to use  salt as photic acid producing agent. salt for example comprises, diazol, phosphonium salt and sulfonium salt, wherein fluoboric acid anion, hexafluoro metaantimmonic acid anion, three fluoro methane sulfonates anion, right-toluenesulfonic acid salt anionic or right-nitrotoleune sulfonate anionic have formed the anion of companion ion.Especially, need photic acid producing agent to contain following general formula (4) and the  salt of (5) expression or the triaizine compounds of halogenation:

R9-C2 ⁺-R10 mA5 ^- …(5)

In the superincumbent general formula, R6-R10 represents the armaticity group respectively and contains in the functional group of chalcogen atom and armaticity group any one that C1 and C2 represent that respectively chalcogen atom, A4 and A5 represent to be selected from PR respectively ₆ ^-, SbF ₆ ^-, BF ₄ ^-, AsF ₆ ^-, CF ₃SO ₃ ^-, C ₄F ₉SO ₃ ^-And CH ₃SO ₃ ^-Anion, m and n represent integer respectively.By the way, on behalf of sulfur family atom and electropositive, term above-mentioned " chalkogenide atom " be higher than the atom of sulfur family atom.Equally, term " sulfur family atom " expression sulphur atom, selenium atom, tellurium atom, polonium atom or iodine atom.

The  salt of top general formula (4) or (5) expression has high solidification reactivity and outstanding stability in room temperature.Curing when consequently, the liquid ink that can suppress one embodiment of the invention with above-mentioned  salt is without light irradiation.

When with the compound of top general formula (4) or (5) expression during,, need sulphur atom or iodine atom to be used as the chalkogenide atom for heat endurance with respect to the stability of water as photic acid producing agent.Simultaneously, in this case, consider acidity and heat endurance, needing anion is non-organic acid, particularly PF ₆ ^-When considering photosensitive property simultaneously, need especially to use to contain the hexafluorophosphoric acid salt compound of phenyl sulfonium skeleton as anionic species.

May need photic acid producing agent also to contain the colouring agent of sensibilization under some situation.The colouring agent of these sensibilizations for example comprises, acridine compound, benzofurabin compound, perylene, anthracene and laser colouring agent.

When using quinone di-azido compound, may need to use the salt of naphthoquinones two nitrine sulfonic acid chlorides and naphthoquinones two nitrine sulfonic acid and so on as photic acid producing agent.

With the compound that can be used as photic acid producing agent organohalogen compound, represent a kind of compound that forms the hydracid of halogenation as example.These organohalogen compounds are described in that for example United States Patent (USP) 3,515,552, United States Patent (USP) 3,536,489, United States Patent (USP) 3,779,778 and West Germany's publication announce the 2nd, 243, No. 621.In specific words, the organohalogen compound that can be used as photic acid producing agent for example comprises, the carbon tetrabromide; four (bromomethyl) methane; ethylene tetrabromide; 1; 2; 3, the 4-tetrabromobutane; the trichlorine Ethoxyethane; right-iodophenol; right-bromophenol; right-iodine biphenyl; 2, the 6-dibromophenol; 1-bromo-beta naphthal; right-bromaniline; chlordene-right-dimethylbenzene; tribromo-acetyl is for aniline; right-bromo-dimethylaniline; tetrachloro 1; 1; 3,4,4; 6-hexamethyl-7-acetyl group-1; 2,3, the 4-naphthane; α; α '-dibromo xylene; α; α ', α, α '-tetrabromo dimethylbenzene; hexabromoethane; the 1-chloroanthraquinone; ω; ω; ω-tribromoquinaldine; hexabromo-cyclohexane; 9-bromine fluorenes; two (pentachloro-) ring penta biphenyl; polyvinyl chloride and 2,4, (they are disclosed in United States Patent (USP) 3 to 6-Trichlorophenoxy ethyl vinyl ether; 515; in No. 552); hexabromoethane; α, α, α tribromo-acetyl benzene; (they are disclosed in United States Patent (USP) 3 to tribromo trichloroethanes and halogenated methyl-S-triazine; in 779, No. 778).Halogenated methyl-S-triazine, as 2, two (the trichloromethyl)-6-S-triazines and 2,4 of 4-, 6-three (trichloromethyl)-6-S-triazine is particularly preferred.In addition, the organohalogen compound that can use on demand comprises vinyl halogenated methyl-substituted compound of S-triazine, and it is disclosed in United States Patent (USP) 3,987, in 037.Vinyl halogenated methyl-S-triazine, this is the photodegradable S-triaizine compounds that contains atomic group (wherein at least one trihalomethyl group and at least one undersaturated ethylenic linkage are interconnected to form triazine ring), represents with following general formula (A):

In the general formula (A), Q represents bromine atoms or chlorine atom, P representative-CQ in the above ₃,-NH ₂,-NHR ,-NR ₂Or-OR, R represents phenyl or contains 6 or be less than the low alkyl group of 6 carbon atoms, and n represents the integer of 1-3, and W represents aromatic ring, heterocycle or with the aryl of following general formula (B) expression:

In the general formula (B), Z represents oxygen atom or sulphur atom in the above, and R1 represents low alkyl group or phenyl.

In the general formula (A), aromatic ring or the substituting group in the heterocycle that W represents can be substituted in the above.Above-mentioned substituting group for example comprises, chlorine atom, bromine atoms, phenyl, contains 6 or be less than low alkyl group, nitro, phenoxy group, alkoxyl, acetoxyl group, acetyl group, amino and the alkylamino of 6 carbon atoms.Simultaneously, the vinyl halogenated methyl-S-triaizine compounds with top general formula (A) expression comprises following compound:

Can suitably use and contain triazine ring (wherein, three halides are introduced into skeleton) as photic acid producing agent.When triazine ring contains two key of at least four conjugation, make the wavelength meeting of compound sensitivity elongated.Therefore, when using conventional high-pressure sodium lamp or similar light source, need to use this compound.Additional disclosure once, above-claimed cpd for example comprises, the compound of triazine and polycondensation triazine.

Can also suitably use and the acid esters of photodissociation ability be arranged as photic acid producing agent.Specific acid esters for example comprises, the aluminium silanol just-the nitrobenzyl ester.

Produce the effect of acid and the amount of the colouring component that in liquid ink, adds according to for example used photic acid producing agent, can determine the content of photic acid producing agent in the liquid ink.For example, when pigment content is about 5 weight %, if the weight of the solvent that is aggregated when existing with acid contained in the liquid ink is 100 parts, then adding photic acid producing agent with the amount of 1-10 weight portion usually, better is the 2-8 weight portion, preferably the 2-6 weight portion.With regard to the storage capacity of printing ink and suppress pipeline and ability that shower nozzle is corroded with regard to, the content of photic acid producing agent should be in above-mentioned scope.Weight with solvent is 100 parts, if the amount of photic acid producing agent less than 1 weight portion, then the sensitiveness of liquid ink will reduce.On the other hand, be 100 parts with the weight of solvent, if the amount of photic acid producing agent more than 10 weight portions, the viscosity of printing ink will increase significantly in time, will reduce the hardness of film forming ability and ink lay after the photocuring process.Simultaneously, the pipeline of recording equipment and shower nozzle might be corroded.

Liquid ink of the present invention can contain as pigment and/or dyestuff as coloring components.Yet, being noted that one of the present invention acid to be used in the embodiment of photopolymerization mechanism that the dyestuff that participant is faded by acid is compared, pigment is preferred.

The pigment that can be used as colouring component is not had any restriction, can use various pigment, as long as this pigment has the colour of required optics to show and painted function.Pigment used in this invention can also have other character, such as show except colour and coloration attributes, can also be magnetic, photoluminescent property, conduction property and dielectric property.These character has been arranged, just can make the image that prints out have various functions.Can also add powdered substance, in order to the hear resistance and the physical property of the liquid ink that improves one embodiment of the invention.

Operable pigment for example comprises, pigment absorption.Pigment absorption for example comprises, is the pigment of base with carbon, as carbon black, CNT; Metal oxide pigment is as iron oxide black, cobalt blue, zinc oxide, titanium oxide, chromium oxide or iron oxide; Sulfide pigment is as zinc sulphide; With the phthalocyanine is the pigment of base; Slaine pigment is as sulfate, carbonate, silicate or the sulfate of metal; And metallic powdery pigment, as aluminium powder, bronze powder or zinc powder.

Organic pigment be can also use, dyestuff chelate, nitropigments, nigrosine, naphthol green B comprised as nitroso pigments and so on; AZOpigments (it comprises azo lake, insoluble AZOpigments, condensed azo pigment and chelate AZOpigments) is as purplish red 10B, C lake red CAN'T 4R or chromophthal red; Mordant pigment is as peacock orchid color lake or rhodamine color lake; Phthalocyanine pigment is as phthalocyanine indigo plant; Many ring pigment are as perylene pigment, perinone pigment, anthraquinone pigment, quinacridone pigment, dioxane pigment, thioindigo pigment, isoindrinone pigment or quinofranone pigment; Durene pigment, red or indatron is blue as thioindigo; Quinacridone pigment; Quinacridine pigment; And isoindrinone pigment.

The pigment that can be used in the black ink for example comprises, Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255 and Raven 7000, and they are made by Colombia Inc.; Regal 400R, Regal 330R, Regal 660R, Mogul L, Monarch 700, Monarch 800, Monarch 880, Monarch900, Monarch 1000, Monarch 1100, Monarch 1300 and Monarch 1400, they are made by CabotInc.; No.2300, No.900, MCF 88, No.33, No.40, No.45, No.52, MA 7, MA 8, MA100 and No.2200B, they are made by Mitsubishi Kagaku K.K.; And the carbon black of Degussa Inc. manufacturing, as Color Black FW 1, Color Black FW 2, Color Black FW 2V, ColorBlack FW 18, Color Black FW 200, Color Black S150, Color Black S160, ColorBlack S170, Printex 35, Printex U, Printex V, Printex 140U, Special Black 6, Special Black 5, Special Black 4A and Special Black 4.

In Yellow ink, can use pigment for example to comprise that Yellow 128, C.I.Pigment Yellow 129, C.I.Pigment Yellow 129, C.I.Pigment Yellow 151, C.I.Pigment Yellow 154, C.I.Pigment Yellow 1, C.I.Pigment Yellow 2, C.I.Pigment Yellow 3, C.I.PigmentYellow 12, C.I.Pigment Yellow 13, C.I.Pigment Yellow 14C, C.I.Pigment Yellow16, C.I.Pigment Yellow 17, C.I.Pigment Yellow 73, C.I.Pigment Yellow 74, C.I.Pigment Yellow 75, C.I.Pigment Yellow83, C.I.Pigment Yellow 93, C.I.Pigment Yellow 95, C.I.Pigment Yellow 97, C.I.Pigment Yellow 98, C.I.Pigment Yellow 114 and C.I.Pigment Yellow 180.In these yellow uitramarines, use PigmentYellow 180 better, because the degree that it fades because of acid causes is lower.

Operable pigment for example comprises in red ink, C.I.Pigment Red 123, C.I.Pigment Red168, C.I.Pigment Red 184, C.I.Pigment Red 202, C.I.Pigment Red 5, C.I.PigmentRed 7, C.I.Pigment Red 12, C.I.Pigment Red 48 (Ca), C.I.Pigment Red 48 (Mn), C.I.Pigment Red 57 (Ca), C.I.Pigment Red 57:1 and C.I.Pigment Red 112.

In addition, the pigment that can be used in the cyan ink for example comprises, C.I.Pigment Blue 15:3, C.I.Pigment Blue 15:34, C.I.Pigment Blue 16, C.I.Pigment Blue 22, C.I.PigmentBlue 60, C.I.Pigment Blue 1, C.I.Pigment Blue 2, C.I.Pigment Blue 3, C.I.PigmentBlue 4, C.I.Vat Blue 4 and C.I.Vat Blue 60.

Chinese white comprises natural clay, metal carbonate such as white lead, marionite and magnesium carbonate, and metal oxide such as barium and titanyl compound also can be used as colouring component.The liquid ink that contains Chinese white not only can be used for the white printing, and can be used for correcting printing, and by rewriteeing the color of revising ground.

Inorganic fluorescent substance or organic fluorescent substance can be used as the pigment with photoluminescent property.Inorganic fluorescent substance for example comprises, the salt of inorganic acid such as MgWO ₄, CaWO ₄, (Ca, Zn) (PO ₄) ₂, Ti ⁺, Ba ₂P ₂O ₇: Ti, BaSi ₂O ₅: Pb ²⁺, Sr ₂P ₂O ₇: Sn ²⁺, SrFB ₂O _3.5: Eu ²⁺, MgAl ₁₆O ₂₇: Eu ²⁺, tungstates and sulfate.On the other hand, organic fluorescent substance for example comprises, the pigment of cyanine series, as acridine orange, aminacrine, quinacrine, anilino-naphthalene sulfonic acid derivant, anthroyloxy stearic acid, rhodamine O, aureomycin, melocyanine and 1,1 '-dihexyl-2,2 '- carbon (oxacrabo) cyanine; The dansyl Cl derivative is as red disulon, red sulphonyl choline, red sulphonyl galacside, red sulphonyl tolidine and dansyl Cl; And diphenyl hexatriene, eosine, ε-adenosine, ethidium bromide, fluorescein, formicin (formisine), 4-benzylamine-4 '-ammonia stilbene-2,2 '-sulfonic acid, the betanaphthyl triphosphoric acid, oxonols pigment, the parinarine derivative, perylene, the N-nonox, pyrene, safranine O, fluorescamine, FIC, the 7-chloronitrobenzene also-2--1, the 3-diazole, red sulphonyl aziridine, 5-(iodo-acetamide ethyl) amino naphthalenes-1-sulfonic acid, 5-iodo-acetamide fluorescein, N-(1-anilino-naphthyl 4) maleimide, N-(7-dimethyl-4-methylcoumarin base (cumanyl)) maleimide, N-(3-pyrene) maleimide, eosine-5-iodo-acetamide, the fluorescein mercuric acetate, 2-(4 '-(2 "-iodo-acetamide) amino naphthalenes-6-sulfonic acid; eosine; rhodamine derivative; organic EL colouring agent; organic EL polymer or organic EL crystallization, and soft meat machine agent (dendrimer).

The powdered rubber that is used for improving ink lay heat resistance and mechanical strength for example comprises the oxide of aluminium and silicon or nitride, filler and carborundum.Simultaneously, the powdered rubber that can add as conductive carbon pigment, carbon fiber, copper, silver, antimony and noble metal and so on makes ink lay have electric conductivity.Iron oxide and ferromagnetic powder can make ink lay have magnetic.Can also add the metal oxide powder that high-k is arranged, as tantalum oxide powder or titanium dioxide powder.

According to one embodiment of the invention, can also in liquid ink, add the auxiliary element of dyestuff as pigment.For example, can in solvent, add acidity and basicity is lower and solubility is higher dyestuff usually, as azo dyes, sulfide (engineering material) dyestuff, disperse dyes, fluorescent whitening agent and oil-soluble dyes.Particularly, oil-soluble dyes are as the auxiliary element that can be used as pigment of azo-type, triarylmethane type, anthraquinone type and piperazine type.Concrete material as the pigment auxiliary element for example comprises, C.I.Solvent Yellow-2,6,14,15,17,19,21,33,56,61,80 etc., Diaresin Yellow-A, F, GRN, GG etc., C.I.Solvent Violet-8,13,14,21,27 etc., C.I.Disperse Violet-1, Sumiplast Violet RR, C.I.SolventBlue-2,11,12,25,35 etc., Diresin Blue-J, A, K, N etc., Orient Oil Blue-IIN, #603 etc., and Sumiplast Blue BG.

Above-mentioned pigment and dyestuff can use separately, and form that also can mixture is used in combination.Can also add above-mentioned pigment and dyestuff simultaneously in order to improve optical absorption characteristics, colourity, colour vision etc.In addition, can use the adhesive of HMW to carry out the dispersive power that processing improves pigment of sealing that microcapsules were handled and prepared in coupling.

Amount that can the 1-25 weight portion is sneaked into colouring component.If the mixed volume of colouring component less than 1 weight portion, then is difficult to guarantee to have enough colour saturations.On the other hand.If the mixed volume of colouring component is greater than 25 weight portions, then the jet performance of printing ink can reduce.The mixed volume of colouring component is preferably in the scope of 2-8 weight portion.

The mixed volume of powder composition should be in the scope of 1-50 weight %.If powder composition mixed volume is less than 1 weight %, then for example the electric conductivity of printed matter is just not enough for the effect of powder.On the other hand, if the mixed volume of powdery metal surpasses 50 weight %, then dissolubility and photosensitivity will reduce.

The average grain diameter of colouring component and powdered rubber should be as much as possible little.The particle diameter of colouring component and powdered rubber be not more than usually atomizing of liquids printing ink nozzle diameter 1/3, be preferably and be about 1/10.What deserves to be mentioned is, said nozzle typically have a diameter from 5 μ m or littler.The particle diameter that is fit to the printing ink jet is 0.35 μ m or littler, and usually, the average grain diameter of colouring component and powdered rubber is in the scope of 0.1-0.3 μ m.

Solvent in the polymerization of following time of sour existence condition mainly is made of the polymerisable compound that above-mentioned feature is arranged." the mainly solvent that is made of polymerisable compound " this statement comprises the solvent that only is made of polymerizable compound, also the solvent that is made of polymerizable compound and the unavoidable impurity of trace.The concentration of the unavoidable impurity of trace must not be higher than 10 weight % in the solvent.Usually be no more than 5 weight %.If the amount of unavoidable impurity exceeds above-mentioned level, remaining solvent will loss in air, bring the problem of secure context, perhaps be retained in the photocuring material, can reduce curing performance.

When having acid to exist crosslinked polymerizable compound the flowability that is no more than 50 ℃ of temperature be not higher than 100cp (=mPas).The polymerizable compound that can satisfy specific demand for example comprises, molecular weight be no more than 1,000 and have above-mentioned substituent acrylic acid or ethylene compounds are arranged on the compound, side chain of cyclic ether group (as epoxide group, oxetane groups or oxorane group), the compound of carbonic ester type, low-molecular-weight melamine compound, vinethene, vinyl carbazole, styrene derivative, AMS derivative, ethene alcohol ester (ester that forms as vinyl alcohol and acrylic or methacrylic acid) and the monomer that contains ethylenic linkage that can cationic polymerization.These polymerisable compounds can be used in combination.

Can contain aliphatic skeleton or cyclic aliphatic skeleton by crosslinked polymerizable compound when having acid to exist, except that above-mentioned polymerizable compound, the above-claimed cpd that adds other also is effective.Specifically, thus so just can increase the transparency of liquid ink in step of exposure makes ink lay that suitable thermoplasticity and dissolubility again be arranged behind photocuring.Therefore, can improve photosensitivity, fixed characteristic, transfer characteristic and maintenance characteristics.Specifically, if polymerizable compound is to be made of the epoxide that has the cyclic aliphatic skeleton, then can satisfy except that reactivity higher boiling and low viscous requirement simultaneously to a certain extent.

In addition, can contain full-bodied compound in the solvent, this compound at room temperature is a solid form, and condition is that less or this compound of the addition of this compound has higher molecular weight.When solvent contains this specific compound, may improve the flexibility of ink lay after the photocuring step and improve the dispersiveness of pigment in ink lay.In addition, if use higher chemical valence and reactive high compound, might improve the hardness and the solvent resistance of ink lay after the photocuring step.These specific compounds for example comprise, molecular weight is less than 5,000 and have cyclic ether group (as epoxide group, oxetane groups or oxorane group, they and the coupling of long-chain alkylidene group) compound, above-mentioned substituent acrylic acid or ethylene compounds are arranged on the side chain, carbonic ester type compound, low-molecular-weight melamine compound, vinethene, vinyl carbazole, styrene derivative, the AMS derivative, ethene alcohol ester (as the ester of vinyl alcohol and acrylic or methacrylic acid formation), contain the monomer of ethylenic linkage that can cationic polymerization and the oligomer that forms by at least a these monomers.

Simultaneously, solvent can also further contain the homopolymers or the copolymer of vinyl alcohol; Molecular weight is lower than 50,000 resin, and described resin contains acid reaction dehydration condensation OH group, COOH group, carboxylic aldehyde group etc., as casein and cellulose; Molecular weight is less than 50,000 polycarbonate resin; The copolymer that contains polyamides propylhomoserin, polyaminoacid or acrylic acid and form at the vinyl compound that has theobromine polymerisable double bond (i.e. polymerisable double bonds in the presence of acid) on the side chain; Vinyl alcohol and on side chain, have the copolymer that the vinyl compound of theobromine polymerisable double bond forms; Except above-claimed cpd, can also contain methylolated melamine.

Specifically, with in the liquid ink contained when acid when existing the weight of polymerisable solvent be 100, if the mixed volume of photic acid producing agent (comprises 1 weight portion and 10 weight portions) between the 1-10 weight portion, and use a kind of pigment as colouring component, then solvent should contain the theobromine polymerizable compound that at least 50 weight portions have aliphatic skeleton and/or cyclic aliphatic skeleton, less than 50mPas, boiling point is higher than 150 ℃ to described theobromine polymerizable compound in room temperature and atmospheric viscosity.

Use has the theobromine polymeric compounds of aliphatic skeleton and/or cyclic aliphatic skeleton, can improve the transparency of printing ink in the step of exposure.Consequently, can make behind the photocuring ink lay have suitable thermoplasticity and dissolubility again, can improve photosensitivity, fixed characteristic, transfer characteristic and maintenance characteristics thus.Particularly, if polymerizable compound is to be made of the epoxide that has the cyclic aliphatic skeleton, then can satisfy higher boiling except that reactivity and low viscous requirement to a certain extent simultaneously.

Be noted that the viscosity that makes under theobromine polymerizable compound room temperature and the atmospheric pressure is no more than 50mPas, can make liquid ink that enough flowabilities are arranged.On the other hand, make the boiling point of theobromine polymerizable compound be not less than 150 ℃, the amount of the contained volatile ingredient of liquid ink is obviously reduced.

When the theobromine polymerizable compound is epoxide, this oxygen compound for example comprises, contain the alkyl compound of (comprising the divalence aliphatic skeleton that contains 1-15 carbon atom or cyclic aliphatic skeleton), or in the divalent group of one or two fatty family chain or cyclic aliphatic skeleton, contain the compound of epoxide group or cyclic aliphatic epoxide group.

As long as contain the epoxide of at least 50 weight portions in the solvent, then satisfy the epoxide of above-mentioned condition and just can bring into play its effect.What can say in passing is, if solvent only is an epoxide, then based on whole liquid inks, requires the amount of solvent (being epoxide) to be no less than 30 weight %, better is to be no less than 40 weight %.If the amount of solvent is less than 30 weight %, nozzle just may get clogged, and thermoplasticity can reduce.

Number to the epoxide group of introducing molecular skeleton does not have any restriction.Yet, in molecular skeleton, should introduce 2-3 epoxide group at most, with the flexibility that guarantees ink lay after the step of exposure and dissolubility again.The compound of general formula (1) or (2) expression below concrete epoxide for example comprises:

R1-A1-R2 …(1)

R3-A2 …(2)

R1-R3 is representative ring oxygen groups or have the epoxide group of cyclic aliphatic skeleton respectively, and A1 and A2 represent functional group respectively.

Conventional viscosity by the compound of top general formula (1) or (2) representative is about 1mPas-30mPas.Therefore, these compounds can effectively reduce the viscosity of liquid ink.Based on the total amount of solvent,, then can bring into play its effect if the low-viscosity epoxy compound is at least 50 weight portions.Yet, be noted that if the low-viscosity epoxy compounds content is excessive, just may hinder the injection of printing ink or the viscosity of increase liquid ink.Under the circumstances, the upper limit of low viscosity epoxy compounds content is no more than 90 weight portions.

Epoxide by top general formula (1) or (2) representative can be used in combination with the cyclic aliphatic epoxide by following general formula (3) expression.Cyclic aliphatic epoxide by general formula (3) representative is full-bodied compound, and its viscosity is about 20mPas-500mPas usually.Therefore, use the epoxide of general formula (3) representative can make ink lay after the photocuring step, have certain flexibility effectively, or have certain degree of hardness on the contrary.

R4-A3-(R5) _k …(3)

R4 and R5 be representative ring oxygen groups or have the epoxide group of cyclic aliphatic skeleton respectively, and it is the functional group of k+1 that A3 represents to contain at least one alkylidene group and/or cyclic aliphatic skeleton and valence mumber, and " k " represents integer.

Spray for realizing the flowability of required minimum requirements, promptly viscosity must not be higher than 30mPas 50 ℃ the time, is 100 with the weight of liquid ink, and for example adding, 50-90 weight portion low viscosity epoxy compound and 10-40 weight portion high viscosity epoxide are favourable.Specifically, the low viscosity epoxy compound is about 1 with the mixed weight ratio of high viscosity epoxide: 1-10: 1.When the low viscosity epoxy compound in this way combined with the high viscosity epoxide, needs used the compound of top general formula (4) or (5) expression as photic acid producing agent, and mixed pigment with the amount of 1-25 weight portion.Like this, just can obtain the liquid ink that all character all are satisfied with, these character comprise the viscosity that is fit to liquid ink and sprays, photocuring character, thermoplasticity and dissolubility again.

Simultaneously, be used in combination with the cyclic aliphatic epoxide, then can improve the curing properties of liquid ink, especially tack if state the epoxide of general formula (6) expression below inciting somebody to action:

R ¹¹-R ¹²-(R ¹¹) _j …(6)

Here, R11 represents that glycidyl ether group, R12 represent to contain the alkylidene group of 1-6 carbon atom or alkylidene group that hydroxyl replaces or contain the alkylidene group of the cyclic aliphatic skeleton that contains cyclic aliphatic skeleton or hydroxyl replacement of 6-15 carbon atom, and j is the integer of 1-3.

The aliphatic epoxy compound for example comprises, the aliphatic epoxy compound, as Celloxide 2021, Celloxide2021A, Celloxide 2021P, Celloxide 2081, Celloxide 2000 and Celloxide 3000, they are made by Dicel Kagaku K.K.; Cyclmer A200 and Cyclmer M100, they are acrylate compounds or the methacrylate compound that contain epoxide group; The methacrylate compound that contains the methyl glycidyl is as MGMA; The glycidol of low molecular weight epoxy compound; Epoxidised soya-bean oil, as β-Jia Jihuanyanglvbingwan, australene oxide, contain 12-14 carbon atom α-paraffin list-epoxide, contain the α-paraffin list-epoxide and the Dimac S-300K of 16-18 carbon atom; Epoxidised linseed oil is as DimacL-500; And multi-functional epoxide, as Epolead GT301 and Epolead GT 401.Can be as the cyclic aliphatic epoxide Cyracure that also has Dow Chemical Inc. (U.S.) to make of aliphatic epoxy compound, this compound is to make by the atomic radical that contains epoxide group in the hydroxyl terminal groups that replaces the low-molecular-weight oxybenzene compound, can make this oxybenzene compound aliphaticization by hydrogenation; The glycidyl ether compound of polyalcohol and cycloaliphatic alcohol (as ethylene glycol, glycerine, neopentyl alcohol, hexylene glycol and trimethylolpropane), and the multi-hydroxy carboxy acid of the aromatic compounds of the glycidol ether of six hydrogen phthalandiones and hydrogenation.

For improving the performance of printing image chemically-resistant material, can add the high and high transparent liquid epoxy resin of Tg value of against weather, as epoxidised polybutadiene, comprise Epolead PB 3600 and PB 3600M that Dicel Kagaku K.K. produces, and EHPE 3150 and EHPE 3150CE.The cycloaliphatic epoxy resin that can also in above-mentioned transparent liquid epoxy resin, add the lactone sex change.The cycloaliphatic epoxy resin of above-mentioned lactone sex change for example comprises, PlaccellGL61, GL62, G101, G102, G105, G401, G402 and G403X, and they are produced by Dicel Kagaku K.K..

Specifically, consider viscosity and volatility, can use Celloxide 2000, Celloxide 3000, australene oxide, by the glycidol ether of alcohols (as neopentyl alcohol, ethylene glycol, glycerine and hexylene glycol) sex change.

Specifically, when mixing selected compound, behind photocuring, can obtain except that photosensitivity the liquid ink that the hardness of ink lay, tack and transfer characteristic are all very satisfied with the mixed proportion of following defined.More particularly, make the mixture of theobromine polymeric compounds contain the cyclic aliphatic epoxide that the 30-70 weight portion has terpene skeleton or norcamphane skeleton, the epoxide of 30-70 weight portion (wherein at least two glycidyl ether groups are formed up to the aliphatic skeleton that contains 6 carbon atoms more), the hexafluoro phosphate compound that contains phenyl sulfonium skeleton of 1-6 weight portion is as photic acid producing agent, and the 1-10 weight portion is as the pigment of colouring component.

Concrete cyclic aliphatic epoxide comprises the compound that is substituted of limonene (two) oxide for example, (two) -bicycloheptane and they.On the other hand, the epoxide that has the aliphatic skeleton that contains 6 carbon atoms at the most for example comprises, neopentyl glycol glycidol ether, DGEEG, glycerine two (three) glycidol ethers and 1,6-hexylene glycol glycidol ether.In these compounds, be used in combination limonene dioxide and neopentyl glycol glycidol ether best.Additional disclosure once, when carbon atom outnumber 6 the time, the hardness of ink lay, tack and transfer characteristic can reduce after the photocuring step.Should be pointed out that if contain the cyclic aliphatic skeleton in this structure at this point, even if then carbon atom outnumber 6, also can keep the hardness of printing ink after the photocuring step.In this case, rise to 15, still can obtain similar characteristic up to the maximum number of carbon atom.The particular compound that addresses that need comprises the bisphenol-A of for example hydrogenation and the glycidyl ether compound of bis-phenol.Yet therefore the common viscosity height of these compounds, is necessary to use the above-mentioned epoxide that contains 6 carbon atoms at the most.

When being used in combination epoxide as stated above, after the photocuring step, ink lay better is that 80 ℃ of quilts liquefy again 50 ℃ minimum temperature, handles and transfer processing so that fix satisfactorily.In addition, in this case, after the photocuring step, can be dissolved in ink lay in the liquid ink once more or be dissolved in the organic solvent of forming by comparatively safe lower alcohol (as ethanol) or by low boiling oil composition (as Isopar).Therefore, so just can overcome the problem of nozzle blockage.And, even if nozzle gets clogged, also solve easily.In other words, can obviously improve the attended operation of shower nozzle.

Determine the characteristic that printed matter is required according to the purposes of printed matter.For example, when the packing of the container that printed matter is made as the packing of can or PET bottle or as oily material, just need printing image that solvent resistance is arranged.In addition, under some situation,, just need higher polymerization speed in order to print with higher speed.

In this case, then except above-mentioned cyclic aliphatic and aliphatic epoxy compound, also need to add epoxide, comprise the glycidyl ether compound and the polyhydroxy styrene of the phenol oligomer of phenolic resins derived from the compound that contains phenolic hydroxyl (being general armaticity epoxide) as the glycidyl ether compound of bisphenol-A.

When need with rice/minute the printing high print speed printing speed, when needing solvent resistance simultaneously, then need to use the armaticity oxetane compound as solvent, it when acid exists, can gather and.Yet, should be pointed out that when mainly using the armaticity oxetane compound, viscosity can obviously raise.Therefore, needs further adding cyclic aliphatic epoxy and/or valence mumber are at least 2 aliphatic or cyclic aliphatic oxetane compound.In this case, the aliphatic oxetane compound can contain the part ehter bond in its chemical constitution.Consider transfer ability and required viscosity, need to add the armaticity oxetane compound of 0-40 weight portion.On the other hand, consider solvent resistance, need to add the epoxide that has the cyclic aliphatic skeleton that is no more than 50 weight portions.In addition, consider to promote the photocuring process that based on the amount of liquid ink, total addition of oxetane compound is at least 40 weight portions.In addition, consider the hardness of ink lay behind the photocuring, the total amount that has the compound of cyclic aliphatic skeleton and armaticity skeleton is at least 30 weight portions.

If the amount of oxetane compound is not in above-mentioned scope, any one in laser curing velocity, transfer characteristic, spray characteristic and the solvent resistance all can be influenced.

Yet, when needing printed matter that higher solvent resistance is arranged, the addition of armaticity oxetane compound can be increased to above above-mentioned scope.Yet, in this case, the increase of viscosity can bring serious problem, therefore, need to use compound that oxetane groups is arranged on the acrylic acid side chain or low viscous compound such as vinethene compound and armaticity oxetane compound to be used in combination.

Valence mumber is at least 2 aliphatic or cyclic aliphatic oxetane compound and for example comprises, two (1-ethyl (3-oxa-cyclobutyl)) methyl ether, 3-ethyl-3-(2-ethyl cyclohexyl methyl) oxetanes, ((1-ethyl-3-oxa-cyclobutyl) methoxyl group) cyclohexane, two ((1-ethyl-3-oxa-cyclobutyl) methoxyl group) cyclohexane, at least one group that contains oxetanes is introduced in the cyclic aliphatic ring and compound such as two ((1-ethyl-3-oxa-cyclobutyl) methoxyl group) norcamphane of making, and at aliphatic polyhydroxy-alcohol such as ethylene glycol, propane diols or neopentyl alcohol, and the alcohol that contains oxetanes, contract as dewatering between 3-ethyl-3-methylol oxetanes and and the ether compound that obtains.

On the other hand, the oxetane compound that contains the armaticity skeleton for example comprises, 1, two ((1-ethyl-3-oxa-cyclobutyl) methoxyl group) benzene, 1 of 4-, two ((1-ethyl-3-oxa-cyclobutyl) methoxyl group) benzene, 4 of 3-, 4 '-two ((1-ethyl-3-oxa-cyclobutyl) methoxyl group) biphenyl and phenolic resin oxetanes.

When use has the acyclic compound of oxetane groups or methacrylic compound on side chain, can also solve the problem that viscosity raises, and picture uses oxetane compound to obtain the effect of photocuring acceleration.

Except improving the solvent resistance of laser curing velocity and printing image, when needing further to reduce viscosity and further improving laser curing velocity, need be in liquid ink separately or the vinethene compound of representing in conjunction with general formula (7) below adding.We know that the cationic polymerization that is attached to the vinethene compound (as the aliphatic ethylene glycol derivative or the cyclohexanedimethanol of vinyl replacement) of the routine on the main body framework by methylene can obviously be suppressed by pigment.In addition, the hardness of photocuring material also can reduce.Pass by in this case to be difficult to the composition of specific vinethene compound as printing ink.Yet even if use simultaneously with pigment, the compound of representing with following general formula (7) (wherein, the vinethene group is to be directly connected on cyclic aliphatic skeleton, terpenoid skeleton or the armaticity skeleton) all has outstanding light-cured performance.For keeping thermoplasticity, based on the amount of all liq printing ink, with the mixed volume of the compound of general formula (7) expression otherwise surpass 50 weight portions.Yet when higher solvent resistance of needs and higher hardness, the total amount that the mixed volume of specific compound can be increased to solvent (when having acid, this solvent can solidify) equates, even if do like this thermoplasticity is affected.

R13-R14-(R13)p …(7)

Wherein, R13 represents at least one vinethene group, and it is the substituting group that is selected from vinethene group and hydroxyl, and R14 represents that valence mumber is the atomic group of (p+1), and it is selected from cycloaliphatic groups and contains the group of aromatic ring, and " p " expression comprises 0 integer.If the cyclic skeleton of R14 representative ring hexane, and " p " be 0, and then at least one carbon atom that forms ring has the ketone structure.

Valence mumber comprises that for the organic group R14 of (p+1) for example valence mumber is the atomic group of (p+1), comprise phenyl ring, naphthalene nucleus or cyclohexyl biphenyl, also comprise umber be (p+1) by its atomic group of deriving, for example cycloalkane skeleton, norcamphane skeleton, adamantane skeleton, tristane (dencane) skeleton, Fourth Ring dodecane skeleton, terpenoid skeleton or cholesterol skeleton.

More particularly, compound with general formula (7) expression for example comprises, cycloaliphatic polyol such as hexamethylene (polynary) alcohol, falls camphane (polynary) alcohol, the three ring last of the ten Heavenly stems (polynary) alcohol, Buddha's warrior attendant (polynary) alcohol, benzene (polynary) alcohol, naphthalene (polynary) alcohol, anthracene (polynary) alcohol and biphenyl (polynary) alcohol; Phenol derivatives, the hydrogen atom in the hydroxyl of these compounds is replaced by vinyl group.Also comprise the compound that the hydrogen atom in the hydroxyl of polyphenolic substance is replaced by vinyl group with the compound of general formula (7) expression, such as polyvinyl phenol or phenolic resin.Even even its hydroxylic moiety keeps some the methylene atoms in inconvenience and the cyclic aliphatic skeleton to be replaced by the substituting group of ketone group and so on.Above-claimed cpd needs, because its volatility reduces.

Specifically, cyclohexyl list vinethene compound has very strong volatility, so when using cyclohexyl list vinethene compound, the hexamethylene epoxy will be turned to the cyclohexanone ring at least.

Can be with several hydrogen atoms on the substituting group substituted ethylene ether of alkyl or halogen atom and so on.

Can prepare above-mentioned vinethene compound with " J.AM.CHEM.Soc. the 124th volume, No., 8 (2002) " the described method of 1590-1591 page or leaf.

In various theobromine polymerizable compounds (i.e. polymerisable compound when acid exists), contain the cyclic aliphatic skeleton, when comprising the terpenoid skeleton, can increase after the photocuring step liquid ink or ink lay like this for human body and environmentAL safety.Concrete epoxide comprises for example laurene, ocimenum, geraniol, nerol, linalool, citronellol, citral, menthene, limonene, dipentene, terpinolene, terpinenes, phellandrene, sobrerone, menthol, terpineol, menthenemonol, isopulegol, pelary aldehyde, menthones, dihydro carvone, carvol, pinol, ascaridole, zabinene, carene, firpene (pimene), bornene (bornene), fenchene, amphene, carbenzol (carbeol), sesquiterpene, diterpene or three amylenes.The terpenes series compound that contains unsaturated bond is used as the initial substance of said derivative, and these derivatives are with unsaturated bond oxidation and epoxidation and form.Can also suitably use by between the pure and mild another kind of alcohol that contains the oxetanes skeleton that contains above-mentioned skeleton, carrying out cyclic aliphatic oxetane compound that dehydrating condensation forms forming ehter bond, and use the vinethene that makes by the hydrogen atom that replaces the alcohol that contains above-mentioned skeleton with vinyl group.On the other hand, epoxide, the oxetane compound of extensive distribution arranged and have the vinethene compound of ENB skeleton, do not need because its price is not high to use at nature.For the compound that has the terpene skeleton is played one's part to the full, the content of these specific compounds is at least 30 weight % and gets final product.

Use the various method for oxidation of oxidant (as peracetic acid) to be used for the oxidation of the preparation epoxide.For example, it is specially suitable using the air oxidation process of N-hydroxyphthalimide and rare earth catalyst.

Liquid ink according to one embodiment of the invention is the photosensitive ink that needs heating, therefore, considers from the angle of safety and smell, needs the volatility of this printing ink lower.In specific words, 80 ℃ evaporation rate should not be higher than 0.2mg/cm after the step of exposure ²Min.This volatile quantity has represented that heating has certain open region (as 10cm ²) container, the volatile quantity of its per minute (mg).It is the amount that 6cm is volatilized when the Petri dish of 4g printing ink is housed that the numerical value of volatile quantity (depending on the area of container open region) is defined as under atmospheric pressure the heating diameter.During heating, the printing ink of forming in above-mentioned scope has extra high evaporation rate.Consequently, its security has been subjected to influence, has produced the problem that strong smell is arranged simultaneously.And, be no more than 0.00001mg/cm as evaporation rate for the obvious lower printing ink of volatility ²The printing ink of min, the viscosity of printing ink is generally bigger, in ink jet process, can make printing ink spray difficulty from nozzle.

As mentioned above, the flowability of the liquid ink of one embodiment of the invention should be at least 30cP (=mPas).For satisfying this particular requirement, the mixture that should contain the above-mentioned theobromine polymerizable compound of n kind (i.e. polymerisable compound when acid exists) in the composition, so that obtain the value of the η t of following formula (1) expression, it is preferably between 5 (mPas) and 25 (mPas) between 3 (mPas) and 30 (mPas):

η _t＝exp(χ ₁·1n(η ₁)+χ ₂·1n(η ₂)+χ ₃·1n(η ₃)+…+χ _n·1n(η _n)) (1)

Wherein, χ ₁, χ ₂, χ ₃χ _nThe mixed proportion of representing each composition weight, η ₁, η ₂, η ₃η _nThe viscosity of each component that expression records under room temperature and atmospheric pressure separately.

If η _tThe scope that do not provide in the above of value in, then be difficult to ejection printing ink.Perhaps, the printing image debase that will be interfered because of the injection of printing ink.

In order to carry out photocuring, use up the liquid ink of irradiation one embodiment of the invention, form ink lay.If ink lay has enough thermoplastic properties and enough solubility properties again after the photocuring step, then the ink lay that forms by atomizing of liquids printing ink on the image-carrier can be transferred on the recording medium.More particularly, after atomizing of liquids printing ink on the image-carrier forms ink lay, use up the ink lay irradiation its curing.Then, ink lay is contacted with recording medium and under this state, ink lay exerted pressure or pressure and heat flow or plasticizing ink lay again, thereby ink lay is transferred on the recording medium.

When being directly injected to liquid ink on the recording medium, can use up irradiation to the ink lay that forms on the recording medium, and heating, ink lay is solidified or precuring.Then, further heating makes its curing to ink lay, and is fixed on the recording medium.

The liquid ink of one embodiment of the invention needs the higher stability in the ink jet direction.Yet the viscosity of liquid ink tends to fast in time and very rising usually, and consequently, this liquid ink is merely able to performance short period of keeping required.In this case, liquid ink should further contain alkali compounds and/or alkalogenic compound as viscosity stabiliser.When carbon black was used as colouring component, viscosity stabiliser can more preferably be brought into play its effect.Alkali compounds can also obviously overcome the erosion of acid in the ink jet head of recording equipment and printing ink tube metal part.Therefore, to use alkali compounds usually in the liquid ink of one embodiment of the invention.

In above-mentioned acid cure compound, can use optional inorganic base and optional organic base, but consider its dissolubility, use organic base better.Organic base comprises for example ammoniacal liquor, ammonium compounds, replacement or unsubstituted alkyl amine, replacement or unsubstituted aromatic amine and the organic amine such as pyridine, pyrimidine and the imidazoles that contain the heterocycle skeleton.In specific words, organic base comprises for example n-hexylamine, dodecyl amine, aniline, dimethylaniline, benzidine, triphenylamine, diazabicyclooctane, diazabicylo hendecane, 3-phenylpyridine, 4-phenylpyridine, rutidine, 2,6-two-tert-butyl pyridine, and sulfohydrazide such as 4-Methyl benzenesulfonyl hydrazine, 4,4 '-oxo two (benzene sulfonyl hydrazide) and 1, the 3-benzene sulfonyl hydrazide.

Can be with ammonium compounds as alkali compounds.Ammonium compounds is the quaternary ammonium salt with following general formula (23) expression preferably;

Wherein, Ra, Rb, Rc and Rd represent alkyl, cycloalkyl, alkaryl or aryl respectively, wherein can replace at least one aliphatic CH with oxygen atom ₂Group, X ₃The expression alkali anion.

In the compound with top general formula (23) expression, Ra-Rd will represent any one group in methyl, ethyl, propyl group, isopropyl, butyl, dodecyl, phenyl and the benzyl, X respectively ₃ ^-The expression be selected from hydroxide ion, ^-OR (wherein R represents the alkyl of C1-C4), ^-OCOR ' (wherein R ' expression alkyl, aryl or alkaryl), OCOO ^-And OSOO ^-Anion.In specific words, should use hydroxylated tetramethyl-ammonium and hydroxylated TBuA compound as general formula (23) expression.Can use a kind of alkali compounds or be used in combination multiple alkali compounds.

Yet, if use strong especially alkali compounds such as imidazoles, difficulty will take place.For example, solvent will be in time and polymerization.Simultaneously, the side reaction of photic acid producing agent decomposition and so on also is easier to take place.On the other hand, when the alkalescence of compound is hanged down especially, then be difficult to obtain enough effects that makes viscosity stabilization by adding this kind alkali compounds.For example, it is comparatively desirable using in the suitable aqueous solution 25 ℃ ionization constant of base pKb to be at least 4 alkali compounds.On the contrary, ionization constant of base pKb surpasses 11 alkali compounds, then is difficult to produce required effect.The alkali compounds that satisfies this specific needs comprises for example pyridine derivate, anil, amino naphthalenes derivative and other nitrogen-containing heterocycle compound and their derivative.

The derivative of pyridine comprises for example 2-fluorine pyridine, 3-fluorine pyridine, 2-chloropyridine, 3-chloropyridine, 3-phenylpyridine, 2-benzyl pyridine, 2-formylpyridine, 2-(2 '-pyridine radicals) pyridine, 3-acetylpyridine, 2-bromopyridine, 3-bromopyridine, 2-iodine pyridine, 3-iodine pyridine and 2,6-two-tert-butyl pyridine.

The derivative of aniline comprises for example aniline, 4-(right-aminobenzoyl) aniline, the 4-benzylaniline, 4-chloro-N, accelerine, 3, the 5-dibromo aniline, 2, the 4-dichloroaniline, N, accelerine, N, N-dimethyl-3-nitroaniline, N-ethylaniline, the 2-fluoroaniline, the 3-fluoroaniline, the 4-fluoroaniline, the 3-Iodoaniline, methylphenylamine, 4-methyl thioaniline, the 2-bromaniline, the 3-bromaniline, the 4-bromaniline, 4-bromo-N, accelerine, the 2-chloroaniline, the 3-chloroaniline, the 4-chloroaniline, 3-chloro-N, accelerine, the 3-nitroaniline, the 4-nitroaniline, the 2-aminoanisole, the 3-aminoanisole, benzidine, 2-benzidine, neighbour-toluidines, between-toluidines, right-toluidines, 3,3 '-DADPS, 4,4 '-DADPS and 4,4 '-two (4-amino-benzene oxygen) diphenyl sulphone (DPS).

Amino naphthalene derivatives comprises for example 1-amino-6-hydroxyl naphthalene, naphthalidine, 2-naphthylamines, diethylamino naphthalene and N-methyl isophthalic acid-naphthylamines.

Other heterocyclic compound and their derivative for example comprise, sinoline, the 3-acetylpyridine, pyrazine, the 2-methylpyrazine, the methylamino pyrazine, pyridazine, the 2-aminopyrimidine, 2-amino-4, the 6-dimethyl pyrimidine, 2-amino-5-nitro-pyrimidine, 2,4,6-triamido-1,3, the 5-triazine, the pyrroles, pyrazoles, the 1-methylpyrazole, 1,2, the 4-triazole, indazole, BTA, quinazoline, quinoline, the 3-aminoquinoline, the 3-bromoquinoline, the 8-carboxyl quinoline, the 3-oxyquinoline, the 6-methoxy quinoline, the 5-methylquinoline, quinoxaline, thiazole, thiazolamine, 3,4-diaza indoles, purine, the 8-azapurine, indoles and indolizine.

In these alkali compounds, consider viscosity, volatility, alkalescence and lower side reaction, it is desirable to use the anil of following general formula (21) expression especially:

Wherein, R ²¹, R ²²And R ²³Can be identical or different, wherein at least one group is represented to replace or unsubstituted aryl, and other group is represented hydrogen atom, hydroxyl, replacement or unsubstituted aryl or replacement or unsubstituted alkyl.

Should be pointed out that the aniline compound with top general formula (21) expression is a low alkalinity.Therefore, this aniline compound and alkaline oxetane compound can not be used in combination.Need to use alkaline oxetane compound, its ionization constant of base pKb of 25 ℃ is between 3 and 7.For example, can use picture to have the amines of aliphatic skeleton, or the alkali compounds of amines and so on cyclic aliphatic skeleton is as oxetane compound.

Equally, when above-mentioned alkali compounds and the anion shown in following general formula (22) form salt, and this anion is weakly acidic, and then this compound self plays weakly alkaline effect, therefore can similarly use this compound:

A wherein ^-Expression contains the compound of sulfonate anionic or carboxyl anion, R ²¹, R ²²-R ²³Can be identical or different, expression hydrogen atom, hydroxyl, replacement or unsubstituted aryl or replacement or unsubstituted alkyl.

Owing to the liquid ink of one embodiment of the invention can be heated after exposure, the volatility of alkali compounds should be low as far as possible.In specific words, the boiling point of this alkali compounds should be not less than 150 ℃, better is not less than 180 ℃.

The amount of the compound of contained alkali compounds or demonstration alkalescence is preferably between 2-15 mole % at 1-30 mole % (based on the total mole number of photic acid producing agent) in the liquid ink of one embodiment of the invention.If the amount of the compound of alkali compounds or demonstration alkalescence is not in above-mentioned scope, then its photosensitivity will significantly reduce, and perhaps this compound can't produce the effect of stable liquid printing ink.

When using under the irradiation of light or radiation resolvent photosensitive alkali compounds, can add photosensitive alkali compounds, because can suppress like this and the reduction that adds the simultaneous photosensitivity of alkali compounds.

Sulfonium compound and iodine  compound can be used as photosensitive alkali compounds.For example, sulfonium compound comprises the compound with following general formula (SS1)-(SS4) expression:

Wherein, R ³¹, R ³²And R ³³Represent alkyl, aryl, heteroaryl respectively or wherein be substituted with aryl, alkaryl, halogen atom, alkoxyl, phenoxy group, thio-phenyl, benzene sulfonyl group or the phenylsulfinyl group of alkyl, Y represents CH ₂, O or S, R ³⁴, R ³⁵, R ³⁶And R ³⁷Represent alkyl, alkoxyl or halogen atom respectively, X1 ^-The expression alkali anion.

Comparatively it is desirable to R ³¹, R ³²And R ³³Represent methyl, ethyl, propyl group, isopropyl, butyl, phenyl, xenyl, tolyl, xylyl, chlorphenyl, bromophenyl, methoxyphenyl, ethoxyl phenenyl, propoxyl group phenyl, butoxy phenyl, tert-butoxy phenyl, Phenoxyphenyl, sulfo-Phenoxyphenyl, sulfo-Phenoxyphenyl and phenyl sulfonyl-phenyl respectively.

Comparatively it is desirable to R ³⁴, R ³⁵, R ³⁶And R ³⁷Represent alkyl, methoxyl group, ethyoxyl, chlorine atom or bromine atoms respectively.

Comparatively it is desirable to X1 ^-The expression anion, comprise hydroxide ion, ^-OR (wherein R represents the alkyl of C1-C4), ^-OCOR ' (wherein R ' expression alkyl, aryl or alkaryl), OCOO ^-And OSOO ^-

In addition, the compound that comparatively it is desirable to use following general formula (IS1)-(IS3) expression is as iodine  compound:

Wherein, R ³⁸And R ³⁹Represent respectively alkyl, aryl, heteroaryl or wherein with any list-, two-or three-replacement form be substituted with the aryl of any one group in alkyl, aryl, halogen atom, alkoxyl, phenoxy group, sulfur phenenyl, benzenesulfonyl, the phenylsulfinyl base, Y represents CH ₂, O or S, R ⁴⁰, R ⁴¹, R ⁴²And R ⁴³Represent alkyl, alkoxyl or halogen atom respectively, the integer of " n " expression 5 or 6, X2 ^-The expression alkali anion.

Comparatively it is desirable to R ³⁸And R ³⁹Represent methyl, ethyl, propyl group, isopropyl, butyl, phenyl, xenyl, tolyl, xylyl, chlorphenyl, bromophenyl, methoxyphenyl, ethoxyl phenenyl, propoxyl group phenyl, butoxy phenyl, tert-butoxy phenyl, Phenoxyphenyl, sulfo-Phenoxyphenyl, sulfo-Phenoxyphenyl and phenyl sulfonyl-phenyl respectively.

Comparatively it is desirable to R ⁴⁰, R ⁴¹, R ⁴²And R ⁴³Represent alkyl, methoxyl group, ethyoxyl, chlorine atom or bromine atoms respectively.

In addition, comparatively it is desirable to X2 ^-The expression anion, comprise hydroxide ion, ^-OR (wherein R represents the alkyl of C1-C4), ^-OCOR ' (wherein R ' expression alkyl, aryl or alkaryl), OCOO ^-And OSOO ^-

Operable sulfonium compound and iodine  compound for example comprise the triphenylsulfonium acetate, hydroxylated triphenylsulfonium, the triphenylsulfonium phenolic ester, hydroxylated three-(4-tolyl) sulfoniums, three-(4-tolyl) sulfonium acetates, three-(4-tolyl) sulfonium phenolic esters, hydroxylated biphenyl iodine , biphenyl iodine  acetate, biphenyl iodine  phenolic ester, hydroxylated pair-(uncle 4--butylbenzene base) iodine , two-(uncle 4--butylbenzene base) iodine  acetate, two-(uncle 4--butylbenzene base) iodine  phenolic ester, the triphenylsulfonium hydroxide that triphenylsulfonium acetate that sulfur phenenyl replaces and sulfur phenenyl replace.

Except above-mentioned concrete alkali compounds, can also add other alkali compounds.When  salt was used as photic acid producing agent, photic acid producing agent and alkali compounds provided comparatively desirable by the cationic components of same kind.When photic acid producing agent and alkali compounds are provided by sulfonium series compound or iodine  series compound, can obtain satisfied photosensitivity and storage stability.

In addition, when the compound that originally is not alkali becomes alkali compounds along with the time decomposition, use this compound comparatively desirable, because the acid that such alkali compounds that forms can neutralize and produce gradually.Can will be able to the time can produce the compound of alkali by heating as this compounds.Concrete compound for example comprises, NBC-101 (trade name is made by Midori Kagaku K.K.) and carbamate compounds, and as α, alpha-alpha-dimethyl-3,5-dimethoxy-benzyl carbamate.Can also use compound with following general formula (TBG1)-(TBG8) expression:

Wherein, R ⁵¹, R ⁵²And R ⁵⁴Represent the alkyl of independently hydrogen atom, the linearity that 1-20 carbon atom arranged or branch or the cycloalkyl of 3-20 carbon atom is arranged, R ⁵¹And R ⁵², R ⁵¹And R ⁵⁴And R ⁵²And R ⁵⁴Can be interconnected to form circulus, R ⁵³Expression has the linearity of 1-4 carbon atom or the alkyl of branch, R ⁵⁵The alkyl of expression hydrogen atom, the linearity that 1-20 carbon atom arranged or branch, the cycloalkyl of 3-20 carbon atom is arranged or the aryl of 6-20 carbon atom is arranged, M represents iodine  or sulfonium, and " j " represents the integer of 2-10, and " k " represents the integer of 1-3.

With R ⁵¹, R ⁵², R ⁵⁴Or R ⁵⁵The linearity with 1-20 carbon atom of expression or the alkyl of branch comprise for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, the tert-butyl group and dodecyl.On the other hand, there is the cycloalkyl of 3-20 carbon atom to comprise for example cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl, ring octyl group and cyclo-dodecyl.In addition, there is the aryl of 6-20 carbon atom to comprise for example phenyl, naphthyl and pyrenyl.In addition, formed circulus comprises for example pyridine radicals, pyrrolidinyl, propyleneimine base and ethyl acetate (acetidino) group.

In addition, with R ⁵³The linearity with 1-4 carbon atom of expression or the alkyl of branch comprise for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl and the tert-butyl group.

In the liquid ink of one embodiment of the invention, can add the dispensed in small quantity agent, as nonionic or ionic surface active agent and the agent of charging lotus, to improve for example dispersing of pigments.Can also suitably use the dispersant of the HMW system that similar characteristics is arranged, as acrylate or vinyl alcohol.Yet, should be pointed out that cation dispersing agent when the dispersant, select the acid compound that is lower than carboxylic acid comparatively desirable.This is because some cation dispersing agent can promote the dark curing reaction of printing ink.Equally, alkaline dispersant and pigment (it can reduce the photosensitivity of printing ink) can promote dark reaction equally.In this case, use neutrality or non-ionic dispersing agent comparatively desirable.

In one embodiment of the invention, when print surface shows strong basicity, perhaps when pigment or print surface can be subjected to sour the influence, can in liquid ink, add the compound that radical polymerization for example can take place and suppress this effect.But the compound of radical polymerization for example comprises, the monomer of acrylic or methacrylic acid monomers, styryl and the vinyl compound that has a plurality of polymerisable atomic groups.Equally, when containing the compound of vinethene series in the liquid ink, this compound combines with acrylic monomers to carry out radical polymerization.In addition, the compound of vinethene series can self radical polymerization.Similarly, can cationic polymerization and during the compound of radical polymerization (CEL2000, the methyl propenoic acid glycidyl ether of producing as Dicel Kagaku K.K. Corp. or the ester type compound that forms by vinyl alcohol and acrylic or methacrylic acid) when in liquid ink, adding, then may obtain can cationic polymerization and the characteristics of radical polymerization.The free radical generation agent (as two-fold nitride) that can in liquid ink, add in this case, photoionization base polymerization initiator (as Michler ' s ketone or the benzophenone of commodity Irugacure by name) and photo-crosslinking type simultaneously.When needing ink lay after the photocuring step, higher solvent resistance to be arranged, can use this technology.

According to as one embodiment of the invention, to prepare liquid ink usually, the feasible content that reduces volatile ingredient in the made liquid ink (as water and organic solvent) as much as possible.Yet, in the liquid ink that is prepared into, contain the organic solvent that in the preparation process of raw material, uses unavoidably, i.e. the solvent of MEK, propane diols series and ethyl lactate etc., this is an acceptable.Equally, being equipped with under the situation of solvent recovery unit for example, for obtaining required printed matter, also can allow to contain a small amount of organic solvent in the prepared liquid ink.In this case, from security standpoint, comparatively it is desirable to make water, alcohol (as ethanol and propyl alcohol) and petroleum component (as Isopar and terpenes).

As mentioned above, the image formation ability of the liquid ink of one embodiment of the invention depends on chemical amplification mechanism.In other words, promptly be that exposure-processed makes photic acid producing agent generate the situation of acid, the acid of Sheng Chenging is spread by heating thus, the effect of catalyst in the performance cross-linking reaction.Therefore, the alkali ion that obviously exists can make the photosensitivity of liquid ink reduce.Therefore, in the process of preparation liquid ink and each component of preparation liquid ink, should take measures to prevent generating a large amount of alkali ions in the liquid ink.

The ink jet recording device of one embodiment of the invention is described below with reference to the accompanying drawings.

Fig. 1 schematically shows the structure of one embodiment of the invention ink jet recording device.As shown in the figure, ink jet recording device 1 comprises the transfering part 3 that is used for shifting recording medium 2.On the direction of motion of transfering part 3, hold towards downstream by upstream extremity, arranging the record head 4, light source 5 of ink-jet type in regular turn and as the heater 6 of heater (heating element heater).

Image among the present invention, recording medium 2 (promptly printing the medium of image) had no particular limits, as long as can be printed on the printed medium 2.In specific words, recording medium 2 comprises for example paper, OHP lamella, resin film, supatex fabric, perforated membrane, plastic plate, circuit board and metallic plate.

Transfering part 3 shifts recording medium 2, makes recording medium 2 in the following sequence in the face of record head 4, light source 5 and heater 6.Shown in the arrow that shows among the figure, among the figure, transfering part 3 shifts recording medium 2 right-to-lefts.Transfering part 3 can be that belt and/or roller form are used for movable recording media 2, and has and drive the transmission device that belt and/or roller are used.Can also be used for assisting moving of recording medium 2 for transfering part 3 provides a guiding parts.

Record head 4 is according to picture signal atomizing of liquids printing ink on recording medium 2, thereby forms ink lay on recording medium 2.Can use the record head 4 of the continuous sweep type that is installed on frame, perhaps width is greater than the record head 4 of the linear scan type of the width of recording medium 2.In order to print at a high speed, the latter is better than the former usually.The method that ejects liquid ink from record head 4 is not particularly limited.For example, can utilize the heat production device to produce water vapor pressure and eject droplet of ink from record head 4, the mechanical pressure of perhaps utilizing piezoelectric element to produce ejects droplet of ink from record head 4.

Use light to be radiated at the ink lay that forms on the recording medium 2, be used in ink lay, producing acid from light source 5.Light source 5 comprises mercury lamp (as low pressure, medium-pressure or high pressure mercury lamp) for example, tungsten lamp, arc lamp, excited quasi-molecular lampbulb, semiconductor laser, YAG (yttrium-aluminium-garnet) laser instrument, unites laser system, high-frequency induction ultraviolet light generating device, electron beam irradiation and the X-x ray irradiation x device of use with laser instrument and nonlinear optical crystal.In specific words, for example comparatively it is desirable to use high-frequency induction ultraviolet light generating device, high pressure or low pressure mercury lamp or semiconductor laser to simplify can make device.Can also on light source 5, load onto condenser or scanning optics.

The ink lay that heater 6 heating forms on recording medium 2 is in order to promote the generation of cross-linking reaction under as the sour existence condition of catalyst.Heater 6 comprises that for example infrared lamp, inside is equipped with the roller (being hot-rolling) of heater element and blows air blast with warm air or hot-air.

By for example said method, with ink jet recording device can be on recording medium 2 printing image.

Among Fig. 1, as first step, recording medium 2 is transferred parts 3 and shifts from right to left.The translational speed of recording medium 2 is set in the scope of 0.1m/min-100m/min for example.

When recording medium 2 was transferred to front surface in the face of record head 4, according to picture signal, liquid ink was ejected on the recording medium 2 from record head 4.The result forms ink lay on recording medium 2.

Then, recording medium 2 further is transported to the front surface in the face of light source 5.When recording medium 2 passed through the front surface of light source 5, the ink lay that forms on the recording medium 2 was penetrated by the illumination of light source 5, and the result has produced acid in ink lay.The intensity of illumination on ink lay surface, it changes with the light wavelength that for example used light source sends, usually at several mW/cm ²To 1kW/cm ²Between.Can suitably set the light quantity of shining ink lay according to the photosensitivity of for example liquid ink and the translational speed of print surface (being the translational speed of recording medium 2).

Then, recording medium 2 is transferred in the heater 6 or the adjacent domain of heater 6.When recording medium 2 passed through heater 6 or passes through the adjacent domain of heater 6, heater 6 added the ink lay that forms on the thermal recording media 2, promoted cross-linking reaction to carry out in ink lay.In the described ink jet recording device 1 of Fig. 1, the heat time heating time of heater 6 is shorter relatively, promptly has only several seconds to tens seconds heat time heating time.Therefore, in order with heater 6 heating the photocuring reaction that carries out in the ink lay to be carried out fully basically, heating should be carried out under higher relatively temperature, but maximum heating temperature is no more than about 200 ℃, be preferably between 80 ℃-200 ℃, or between 60 ℃-180 ℃.

Then, recording medium 2 is transferred in the container (not shown), promptly finishes printing operation.

The heater of heating ink lay is not limited only to the heater 6 that is contained in light source 5 back as shown in Figure 1.For example, make and its adjacent domain that is positioned at recording medium 2 is moved light source 5 can at this moment, in the step that ink lay is exposed to light, just can not damage print surface like this with light source 5 as thermal source.Can also in light source, not load onto heat removal apparatus (as cold mirror), so also can be with this light source as thermal source.When using the output lamp with high bubble of several hectowatts, this bulb also comprises a cooling device.Therefore, heat removal apparatus can partly be revised, and loads onto the device that can intentionally heat be turned back on the paper in bulb.The heat that the result can utilize light source to produce heats ink lay.

Specifically, an above-mentioned output lamp with high bubble is for example exported the light source greater than 100W, and it comprises that imports the device that air stream is used for cooling off light source, and this air stream turns back on the paper surface then or enters transfer/bracing or strutting arrangement and heats.The heat that is returned by light source is enough to recording medium is heated to the temperature that heats basically identical with above-mentioned heater and gets final product.The temperature of recording medium need reach at least 60 ℃ usually, is more preferably to reach 80-100 ℃.Simultaneously,, can under about 180 ℃ high temperature, heat, because heating is carried out immediately when for example several m/sec at full speed expose.

Except visible light as light source 5, also use when can launch for example ultrared light source, just can heat simultaneously light-struck.Because can promote photocuring, therefore use such light source better.

If ink lay is penetrated by illumination, the heat heating that ink lay is produced by light source 5.The result needn't adorn one as the heater of heater 6 as parts independently.Yet when ink lay was placed room temperature, at this moment ink lay was only solidified by the heat that light source 5 produces, and needed long heat time heating time that ink lay is solidified fully.Therefore, if before solidifying fully, can guarantee the sufficiently long time, just need to use the device that allows ink lay stop in room temperature.For example, if the printed advertising of delivering with newspaper next day can guarantee 4-24 hour long hardening time.In this case, even if make ink lay be retained in room temperature, ink lay is solidified fully.

Fig. 2 shows the structure of light source 5 as the ink-jet recording apparatus 1 of thermal source heating ink lay.In the ink-jet recording apparatus of Xian Shiing, provide the air blast 8 of gaseous material (air) to be connected in light source 5 in the drawings, have individual blast pipe (gaseous material passage) 9 to place between light source and the air blast.When air that air blast provides by light source 5 this by the heat exchange heating air so that flow on the ink lay that forms on the recording medium 2, therefore, when using up the irradiation ink lay, ink lay just is heated simultaneously.

The ink jet recording device that shows among Fig. 2 can be revised according to Fig. 3.In the ink jet recording device that shows in Fig. 3, heating mantles 10 (gaseous material after the heat exchange is introduced into wherein) is connected with light source 5 by blast pipe 9.After illumination was penetrated, the recording medium 2 that has ink lay was transferred in the heating mantles 10, and the results ink layer is heated.When using this structure, can make full use of the gaseous material heating ink lay after the heating.

When light source 5 produces infrared ray together with visible light, can be with infrared ray directly as thermal source.Fig. 4 exemplarily represents the ink jet recording device of this structure.In the ink jet recording device shown in the figure, there is the light source 5 of thermal source effect to be contained in the back of record head 4 simultaneously.Fig. 5 is the schematic cross-section of the structure of light source 5.

As shown in Figure 5, not only can uv reflectance and also reflecting plate 12 that can reflected infrared ray place lamp 11 tops, the window 13 that allows ultraviolet ray and infrared ray to pass through places the below of lamp 11.The infrared ray direct irradiation that the ink lay that forms on the recording medium is produced by light source 5, thereby heating ink lay.Infrared reflection plate 12 and the window 13 that allows ultraviolet ray and infrared ray to pass through be used in combination to be enough to raising and to add thermal effect.Yet, also can use any one in infrared reflection plate 12 and permission ultraviolet ray and the window 13.

Can in the container that a plurality of recording mediums through illumination are housed, heat with this heating means.

Fig. 6 schematically shows the structure of another embodiment of the present invention ink jet recording device.The structure of the ink jet recording device 1 that shows among the ink jet recording device 1 that shows among Fig. 6 and Fig. 1 is basic identical, and difference is, in the container 7 of the shown equipment of Fig. 6 heater is housed.

Container 7 can pack into a plurality of through the exposure recording mediums 2, and can allow recording medium 2 be not less than for example about 40 ℃ temperature maintenance certain hour through exposing, the ideal temperature of insulation is between about 50 ℃-120 ℃, better is between about 60 ℃-100 ℃, or between about 50 ℃-80 ℃.

In equipment shown in Figure 11, heater 6 is placed in the transmission distance of recording medium 2, therefore, is difficult to the single recording medium 2 of long-time heating.Yet in equipment shown in Figure 61, heater places container 7, therefore, and can each recording medium 2 of long-time heating.In addition, heat, consider that from the energy consumption aspect this structure also is favourable owing to can in container 7, hold a plurality of recording mediums 2.In addition, because can each recording medium 2 of long-time heating, other advantages described as follows can be obtained.

Specifically, because short time heating at high temperature can impel the liquefaction again of ink lay, can destroy the printing image, and this depends on recording medium 2 and used liquid ink.Because the destruction of printing image is owing to liquefying again of ink lay under the high temperature caused, so long-time heating can prevent this destruction to the printing image under relatively low temperature.For example, will through the recording medium 2 of overexposure in container 7 about 50 ℃-80 ℃ keep a few minutes at least, ink lay solidified fully and do not damage the printing image.

Container 7 preferably can be equipped with a discharger, is used for discharging in succession the recording medium 2 that scheduled time heated.According to the heating-up temperature of for example used liquid ink, can determine that recording medium 2 keeps the time of heating.When heating-up temperature being set in for example 50-100 ℃, it is comparatively desirable to be set at about 0.5-10 minute heat time heating time.On the other hand, when not being when heating by heater, recording medium 2 can be kept the time set of heating be several hrs.

As shown in Figure 1, can further heater 6 be contained in the front of container 7.If ink lay does not solidify fully before a plurality of recording mediums 2 are transferred to container 7, they will damage the printing image when contacting with each other in container 7.If heater 6 is placed container 7 fronts, can overcome damage to the printing image, this is because before recording medium 2 is put into container 7, heater 6 each recording mediums 2 of heating.

Fig. 7 exemplarily shows the structure of another embodiment of the present invention ink jet recording device.In the ink jet recording device 1 that shows in Fig. 7, air blast 8 is connected with light source 5 by blast pipe 9, and air is carried out heat exchange.Air by the heat exchange heating feeds the container 7 that is equipped with through light-struck recording medium through blast pipe 9.In this way, can in container 7, use the hot air ink lay.

Fig. 8 shows the structure of another embodiment of the present invention ink jet recording device.The ink jet recording device 1 that shows among this figure has used by frequency electromagnetic waves luminous light source 5.Light source 5 is coated in the electromagnetic shield 15 that is connected with high frequency generating apparatus 14, only stays its surface facing to transfering part 3.The heat production medium 16 of generation heat places the zone, the back side in the face of the transfering part 3 of light source 5 under the irradiation of frequency electromagnetic waves.Not necessarily electromagnetic shield to be placed on around the bulb.According to circumstances can cover armamentarium with electromagnetic shield.Heat production medium 16 can be made by for example microwave heating ceramic material, microwave heating silicone resin or boiling device.In addition, if this ceramic material or silicone resin are ground into powder, and this powdered rubber is mixed liquid ink, printing ink self just can produce heat, therefore just can save heat production medium 16.

The frequency electromagnetic waves that high frequency generating apparatus 14 produces makes light source 5 luminous, the frequency electromagnetic waves irradiation that the device 16 of heat production is simultaneously produced by high frequency generating apparatus 14.As a result, heat production device 16 produces heat adds thermal recording media 2 surface formation by transfering part 3 ink lay.

When transfering part 3 is when being made by high frequency heat production material, transfering part 3 has the effect of heat production medium 16.Therefore, not necessarily want image pattern 8 such, heat production medium 16 is placed transfering part 3 back sides separately.Can use the magnetron of using in the conventional electric cooking oven as high frequency generating apparatus.The high-frequency electromagnetic wave frequency of Chan Shenging generally is about 2.45GHz in this case, and input power is about 0.3kW.The light source of obtainable said structure comprises for example Light Hammer series of products of Fusion UV Syetem company manufacturing on the market.

One embodiment of the invention ink jet recording device can be equipped with a plurality of record heads that can spray the different colours liquid ink, is used for making the recording equipment that is fit to colored printing.Fig. 9 exemplarily represents the structure of the ink jet recording device 1 of suitable colored printing.

The ink jet recording device 1 that shows among Fig. 9 is equipped with four record heads that can spray different colours (being cyan ink, Yellow ink, magenta ink and black ink) liquid ink.What be contained in each record head back is the light source 5 that is connected with air blast 8 by blower 9 as mentioned above.Therefore, form ink lay from record head, just carry out illumination and penetrate and/or be heated to each ink lay if liquid ink ejects at recording medium 2.Need this specific device, because the printing ink that it can obviously overcome because of different colours mixes irregular colour one property that causes.Yet, should be pointed out that under some situation that some printing ink that contains fragrant oxetane compound or aromatic ethylene ether compound is difficult to only mat light hardening with radiation.At this moment, not necessarily to spray a kind of color ink, and the ink lay that forms is carried out all heating after illumination is penetrated each time.In other words, can once heating always in final step.

Figure 10 schematically shows the structure of another embodiment of the present invention ink jet recording device.The ink jet recording device 1 that shows among this figure has a bulging 18a as image-carrier.Among the figure, drum 18a can be rotated by drive unit (not shown) clockwise direction.Arrange record head 4, light source 5 around the 18a in the direction of the clock in regular turn at drum, as the heater 6 of heater, as the transfer roller 19 and the cleaner 20 of transfer device.In addition, transfering part 3 also being housed can insert in the gap between bulging 18a and the transfer roller 19 recording medium 2.

Face the surface of the bulging 18a of record head 4 grades, the surface of promptly carrying image, thus should be by printing ink, pressure, light and heat being had enough resistances and having enough fissilities image transfer can be made to recording medium 2 lip-deep materials.The material that satisfies this requirement comprises for example metal and polytetrafluoroethylene (PTFE).Simultaneously, can also have to form on the surface of image at drum 18a and contain photochemical catalyst (as TiO ₂) layer.In this case, the hydrophily of exposure stage can increase, in order to improve the ability of control wetability and fissility.Simultaneously, carry a black ability and a fissility, on drum 18a has the surface of image, use the sheet of Teflon or derivatives thereof, preferably PTFE (polytetrafluoroethylene (PTFE)) porous chips in order to improve.

Transfer roller 19 is exerted pressure to itself and the recording medium 2 of drum between the 18a, and normally pressure and heat are transferred to ink lay on the recording medium 2 from drum 18a.Usually, in transfer roller 19, heater is housed, can add thermal recording media 2 in the transition phase of ink lay, but the maximum temperature that recording medium can reach is no more than 200 ℃, be preferably between about 60 ℃-180 ℃.When in the transfer roller 19 heater being arranged, transfer roller 19 has played and has promoted the effect that ink lay solidifies.

Because the ink lay after the transition phase does not solidify fully, an end that need be positioned at the route of metastasis downstream on transfer roller 19 refills a heater.Perhaps, can use the foregoing container 7 that has heater.

Not necessarily to load onto cleaner 20.Yet, under the situation that cleaner 20 is housed, can there be the surface of image to clean to drum 18a, can obtain high-quality printed matter.Can use, for example scraper or wiper are as cleaner 20.

Can revise the structure of Figure 10 in various manners.For example, can be used in combination a plurality of bulging 18a and avoid phase mutual interference between each component parts.Simultaneously, do not make the ink lay of transferring on the recording medium 2 impaired, can in ink-jet conclusion equipment 1 shown in Figure 10, further install heater 6 shown in Figure 1 and/or the container that is covered with heater 7 shown in Fig. 6 for curing.In addition, as mentioned above, light source 5 and heater 6 can be used in combination, form a overall structure as light source and thermal source.

The operating condition of ink-jet recording apparatus 1 shown in Figure 10 is as follows.

Use the aluminium drum 18a of diameter 250mm, this aluminium drum 18a is with the circumferential speed rotation of 25m/min.Record head 4 can spray the oil droplet of about 40pL with the dot density of 300dpi.The F300 type ultraviolet source that Fusion UV System company makes is used as light source 5.The centre wavelength of light source 5 is 360nm, and light source 5 is output as 150W/cm.The QIR-105 type halogen lamp heater that NipponHeater K.K. makes is as heater 6.The maximum of the radiant-energy spectrum of heater 6 is between 0.9 μ m and 1.6 μ m.Lamp is output as 500W, and length is 225mm, and effective length is 155mm, and diameter is 10mm.

Figure 11 schematically shows the structure of another embodiment of the present invention ink jet recording device.The ink jet recording device 1 that shows among Figure 11 has the endless belt 18b of bar as image-carrier.Endless belt 18b is stretching around a plurality of roller 21.Among the figure, by the drive unit (not shown), roller 21 can rotate in the direction of the clock.Among the figure, along with the rotation of these rollers 21, endless belt 18b rotates in the direction of the clock.Around the endless belt 18b by following clockwise direction arranging record head 4, light source 5, heater 6 in regular turn, as the transfer roller 19 and the cleaner 10 of transfer device.In addition, transfering part 3 is housed also, recording medium 2 can be inserted in the gap between endless belt 18b and the transfer roller 19.

Face the surface of the endless belt 18b of record head 4 grades, the surface of image is promptly arranged, thus should be by printing ink, pressure, light and heat amount being had enough resistances and having enough fissilities image transfer can be made to recording medium 2 lip-deep materials.The material that satisfies this requirement comprises for example metal and polytetrafluoroethylene (PTFE).Can also carry to form on the surface of image at drum 18a and contain photochemical catalyst (as TiO ₂) layer.In this case, the hydrophily of exposure stage can increase, in order to improve the ability of control wetability and fissility.

When endless belt 18b is used as image-carrier, can make a part of carrying the picture strip sub-surface smooth, the result can be easy to by a plurality of record heads 4 of arranged in series and record head 4 is tilted by direction of rotation.Simultaneously, even if the girth of endless belt 18b is very long, because the suitable roller 21 of having installed, can relatively freely arrange record head 4 and other parts.Consequently, when endless belt 18b is used as image-carrier, can improve the free degree of design.

Structure shown in Figure 11 can be revised in various manners.For example, can be used in combination a plurality of endless belt 18b and avoid phase mutual interference between each component parts.Simultaneously, do not make the ink lay of transferring on the recording medium 2 impaired, can in ink-jet conclusion equipment 1 shown in Figure 11, further install the container 7 that is covered with heater shown in heater 6 shown in Figure 1 and/or Fig. 6 for curing.

The operating conditions of ink-jet recording apparatus 1 shown in Figure 11 etc. are as follows.

Use the stainless steel endless belt 18b of girth as 760mm.The circumferential speed of endless belt 18b is set at 25m/min.Use can be sprayed the record head 4 of about 40pL oil droplet with the dot density of 300dpi.In addition, used light source 5 and heater 6 are respectively the F300 type ultraviolet source of Fusion UV System company manufacturing and the QIR-105 type mercury lamp heater that Nippon Heater K.K. makes, and this was just mentioning in the narration of Figure 10.

In Figure 10 and Figure 11, all shown the heater 6 that is used for ink jet recording device.Yet heater is not limited to heater 6.As previously mentioned, can light source 5 be used as thermal source by various technology.Can also use a plurality of record heads that can spray different colours printing ink to carry out the polychrome record.The direction of rotation that can follow the usual practice as image-carrier is discharged to a plurality of record heads.In this case, light source and heater are placed in the tight back of each record head respectively.Perhaps, a plurality of record heads can be placed on same position, and single source and single heater are installed.In specific words, the liquid ink of first kind of color sprays from a record head and forms ink lay, uses up the irradiation ink lay subsequently and heats ink lay with heater.Rotating image carrier then, the liquid ink of second kind of color ejects the formation ink lay, carries out illumination and heating with this same light source and this heater subsequently.Aforesaid operations is repeated required number of times, form requisite number purpose ink lay, and carry out illumination and add the ink lay of the multiple color of thermosetting one deck.Should be pointed out that as previously mentioned some printing ink has higher light-cured performance.In this case, can shades of colour is printed with exposure-processed after, once carry out total heat treated.In addition, when image for example is printed on the absorbing medium, can significantly suppress the mixing of color.And can spray the liquid ink of multiple different colours simultaneously, then the ink lay that forms full-colour image is exposed and heat treated realizes panchromatic printing.The liquid ink of one embodiment of the invention also is favourable at this on the one hand, because the printing ink that is permeating also can fully solidify.

In above-mentioned ink jet recording device 1, load onto the device that shifts recording medium 2, recording medium 2 is moved with respect to record head 4 grades.Perhaps, can allow recording medium 2 keep motionless and moving recording head 4 etc.All right movable recording media 2 and record head 4 etc. simultaneously.The device that record head 4 grades are moved is favourable for going up the formation ink image at three-dimensional record medium 2 (as bottle or jar).In addition, the said equipment not only can be used as printing press, and can be used as duplicator.

As previously mentioned, be used for the pigment of one embodiment of the invention liquid ink, can chromatic colour show and painted characteristic and as other character of magnetic, photoluminescent property, conduction property, dielectric property and electromagnetism generation heat character etc. and so on.When use contains the liquid ink of this specific pigment, can make print product that multiple function is arranged.Some examples of liquid ink will be described below.

First example is to use the liquid ink that contains magnetic pigment.In this case, preparation contains the liquid ink of magnetic pigment powder.Can with photic acid producing agent and high-molecular weight compounds or HMW powdered rubber (being used for improving dispersibility) together, in above-mentioned solvent, add Magnaglo (as the powder of iron, cobalt, nickel and their alloy or its oxide), can make this special liquid ink thus.

In following step, with this liquid ink to represent that for example the mode of bar code is ejected on the recording medium.Behind the atomizing of liquids printing ink, the light source with ultraviolet light and so on shines ink lay immediately.Hand over exposure to depend on the photosensitivity of the content and the liquid ink of pigment in the liquid ink, be generally hundreds of mJ to one thousand hundreds of mJ.The viscosity of ink lay and mobile disappearance immediately after illumination.Yet, if ink lay put into temperature is controlled at container between the room temperature to 60 ℃, ink lay is solidified fully.Because in this mode, the ink lay of curing is magnetic, and then can also read second information by the magnetic detection device of magnetic head and so on except that image information.

Second example is to use the liquid ink that contains the pigment that electric conductivity is arranged.In this case, prepared to have the liquid ink of electroconductive powder material as pigment.Can with photic acid producing agent and high-molecular weight compounds or HMW powdered rubber (being used for improving dispersibility) together, in above-mentioned solvent, add conductive pigment, powdered rubber as the alloy of silver, gold, copper, aluminium, carbon, nickel, iron, cobalt, lead, tin, antimony and some of them metal, and the composite that contains these powdered rubbers and organic substance, can make this liquid ink thus.Increase the electric conductivity of ink lay by reducing resinous amount in the final gained ink lay, can reduce the amount of contained polymerizable compound in the liquid ink, and in liquid ink, add organic solvent.

In following step, liquid ink is ejected into the pattern that forms on recording medium such as the insulating substrate as wiring diagram and so on.Behind the ink jet, the light source with ultraviolet light and so on shines ink lay immediately.The illumination amount of penetrating depends on the photosensitivity of the content and the liquid ink of pigment in the liquid ink, is generally hundreds of mJ to one thousand hundreds of mJ.The viscosity of ink lay and mobile disappearance immediately after illumination.Yet, if ink lay put into temperature is controlled at container between the room temperature to 60 ℃, ink lay is solidified fully.And, if to ink lay heating with exert pressure, can further improve electric conductivity.In addition, if the alloy powder that fusing point is lower when the conducting pigment, can be heated to ink lay the temperature that fusing flows and obtain conductive pattern.Thus obtained printing image has electric conductivity, can be used as circuit pattern or resistance pattern.

In addition, use with dielectric powder (as, barium, lead, bismuth, ruthenium, tantalum, platinum, titanium, strontium, chromium, their alloy or the powder or the ceramic powders of oxide) as the liquid ink of pigment, can form the dielectric layer of capacitor or inductor.Improve performance if like this, can according to circumstances form the back by calcining at image.Simultaneously, if use the liquid ink that contains pigment (as titanium oxide powder), then can form printing image with this effect with photocatalysis or bactericidal action.The powder that electromagnetism produces heat comprises for example ceramic masses and silicone resin, and it can be used to by electromagnetic wave printed patterns be carried out the selectivity heating.This powder can be used to improve the general electromagnetic heating performance of one embodiment of the invention liquid ink.

In addition, suitable is used in combination above-mentioned technology and embodiment of the present invention, can realize overlapping printing and print the bigger image of thickness.In specific words, on the presumptive area of recording medium, spray several times printing ink and solidify the gained ink lay, the effect that can obtain giving prominence to repeatedly.For example, can partly correct the printing image, be formed with the image of bossing, form the printed matter that characters cut in relief and so on uses for the disabled person so that rely on the tactile discrimination image, printed matter such as map that formation changes according to outline line thickness, and the device that forms the not little many microns of a part of thickness.

To use some embodiments of the present invention to describe embodiment of the present invention in detail below.

Example I

Example I-1

By the mixed proportion that table 1 is listed, mix theobromine polymerizable compound given below can be under sour existence condition polymeric compounds (and resin) Ep1-Ep16, prepare composition a1-j1.

Above l, m and the integer of each representative of n in the 1-20 scope in all general formulas.

Table 1

Epoxy composite	Epoxide (weight %)
					a1	Ep3(100)
b1	Ep3(87.5)	Ep11(12.5)
					c1	Ep3(80)	Ep11(10)	Ep16(10)
d1	Ep2(70)	Ep10(20)	Ep12(10)
					e1	Ep1(80)	Ep9(10)	Ep16(10)
f1	Ep7(50)	Ep3(30)	Ep10(10)	Ep16(10)
					g1	Ep3(40)	Ep8(30)	Ep13(10)	Ep14(10)
h1	Ep3(40)	Ep4(40)	Ep11(12.5)	Ep15(7.5)
					i1	Ep6(50)	Ep3(30)	Ep11(10)	Ep16(10)
j1	Ep5(30)	Ep3(40)	Ep12(20)	Ep15(10)

According to shown in the following table 2 prescription, in each composition a1 to j1, add pigment and photic acid producing agent, use the coating shaking machine to carry out dispersion treatment 24 hours.Use the mixture after 5 microns PTEF filter filters dispersion treatment, obtain liquid ink (1) to (20).

Table 2

Liquid ink	Epoxy composite	Pigment (weight %)	Acid producing agent solution (weight %)
				(1)	a1	BL(5％)	PAG5(8％)
(2)	b1	BL(5％)	PAG5(8％)
				(3)	c1	BL(5％)	PAG5(8％)
(4)	d1	BL(5％)	PAG5(8％)
				(5)	e1	BL(5％)	PAG5(8％)
(6)	f1	BL(5％)	PAG5(8％)
				(7)	g1	BL(5％)	PAG5(8％)
(8)	h1	BL(5％)	PAG5 (6%)+Iruga solidifies (2 %)
				(9)	i1	BL(5％)	PAG5(8％)
(10)	j1	BL(5％)	PAG5 (6%)+Iruga solidifies (2 %)
				(11)	b1	Y(5％)	PAG5(8％)
(12)	b1	C(5％)	PAG5(8％)
				(13)	b1	M(5％)	PAG5(8％)
(14)	b1	BL(5％)	PAG5(4％)
				(15)	b1	BL(5％)	PAG5(16％)
(16)	b1	BL(5％)	PAG1(8％)
				(17)	b1	BL(5％)	PAG2(8％)
(18)	b1	BL(5％)	PAG3(8％)
				(19)	b1	BL(5％)	PAG4(8％)
(20)	b1	BL(10％)	PAG5(8％)

Use carbon black, C.I. pigment Yellow 12 8, C.I. pigment blue 15 and C.I. pigment red 123 respectively as black pigment, yellow uitramarine, cyano group pigment and magenta pigment.In all cases, the pigment of crumbing in advance prepares the material of crumbing, and the material of crumbing that obtains is added in the epoxy composite with 200ppm non-ionic surface active agent (Sumitomo 3M Inc. manufacturing).According to energy dispersive, in epoxy composite, add the dispersant A jisper (trade name is made by Ajinomoto Fine Technology Inc.) that buys.

The compound of chemical formulation adds photic acid producing agent as photic acid producing agent PAG1 to PAG4 with the solution form below using, and the preparation of this solution is that photic acid producing agent is dissolved in the propyl carbonate with 50% concentration.

Use solution " UVACURE 1591 " that Dicel UCB Inc. makes as PAG5, this is that mixture with PAG1 and PAG2 is dissolved in the solution that propyl carbonate makes with 50% concentration.

The liquid ink of preparation induced generation free radical type is to compare.Particularly, mix 5 parts by weight of acrylic acid isobornyl thiocyanoacetates, 25 weight portion diacrylate tripropylene glycol esters and 15 weight portion trimethylolpropane ethoxylation triacrylates.Then, the acrylic dispersants and the surfactant that in the mixture that makes, add 5 weight portion Irugacure (No.2959, Nagas Sangyo K.K. makes), 5 weight portion charcoal blacks and trace.The mixture that obtains was used the homogenizer dispersion treatment 5 hours, subsequently with the mixture of 5 microns PTEF filters filtrations through homogenizing.Thus obtained induced generation free radical type liquid ink is called liquid ink (21) at this.

For comparing example, also prepared solid ink.Particularly, the heat fused mean molecule quantity is 3000 alkane, in temperature keeps 100 ℃ the alkane of fusing, adds charcoal blacks and trace acrylic dispersants and surfactant.The homogenizer of heating element heater is equipped with in use, at 100 ℃ obtaining mixture is carried out 5 hours dispersion treatment, under 100 ℃ heating condition, use fritted glass filter that the composition that makes is filtered, with the filtrate cooling, obtain solid ink subsequently, be referred to herein as liquid ink (22).

Use Fig. 1 and each ink jet recording device shown in Figure 6, liquid ink (1) to (21) is carried out performance test.Use common glazed paper as recording medium 2, use power output as the ultrahigh pressure mercury lamp of 230W as light source 5.The injector head temperature is 45 ℃.

Measure the ink lay pencil hardness and the printing quality of liquid ink (1) to (21).Table 3 is listed exposure energy and test result.

Table 3

Liquid ink	Exposure energy mJ/cm 2	Pencil hardness				Situations such as printing quality
							After the exposure at once	Container	Room temperature leaves standstill	Hot-rolling
		(1)	340	B	H						H	Avalanche	Smudgy
(2)	450					B	F	F	HB	Good especially
		(3)	500	B	F						F	F	Good especially
(4)	640					2B	HB	HB	HB	Well
		(5)	750	2B	B						B	Avalanche	Smudgy
(6)	540					B	H	H	HB	Good
		(7)	340	HB	H						H	H	Printed layers shows high solvent resistance
(8)	750					B	F	F	F	Paper shows alkali resistance
		(9)	450	B	F						F	F	Well
(10)	600					B	F	F	HB	Paper shows alkali resistance
		(11)	350	B	F						F	HB	Good especially
(12)	400					B	F	F	HB	Good especially
		(13)	270	B	F						F	HB	Good especially
(14)	450					2B or littler	B	F	B	Fuzzy
		(15)	450	2B or littler	B						B	B
(16)	350					B	F	F	F	Good especially
		(17)	780	B	F						F	F	Good especially
(18)	800					2B or littler	F	F	F
		(19)	1000	2B or littler	F						F	F
(20)	900					B	F	F	F	Well, thick
		(21)	1750	Do not solidify	Do not solidify						Do not solidify	Do not solidify

Pencil hardness in the table 3 is meant under below the condition measured value to ink lay.

After the exposure at once: exposure back ink lay state at once.

Container: the ink lay that uses printing machine shown in Figure 6 to form.After the exposure, ink lay in this container 80 ℃ kept 3 minutes.

Room temperature leaves standstill: after the exposure, ink lay room temperature (25 ℃) left standstill 8 hours.

Hot-rolling: after the exposure, ink lay is heated with the hot-rolling that is heated to 160 ℃.

Using induced generation free radical type liquid ink (21) situation, ink lay is being solidified although significantly increase light exposure, as shown in table 3.For can be with 1,000mJ/cm ²Exposure energy come the cured printing ink layer, the pigment concentration of liquid ink must be reduced to 3 weight %.Pencil hardness in this case is HB, and the printed matter color and luster of acquisition is shallow, has strong resinous luster.

On the other hand, using arbitrary liquid ink (1) to (20) situation, can under less relatively exposure energy and various heating condition, solidify this ink lay.The photosensitivity of liquid ink (1) to (20) all is 1.5-3 times with respect to liquid ink (21).And, use arbitrary liquid ink (1) to (20) situation, printed matter do not have photosensitive ink intrinsic resinous luster, therefore can be satisfactory.If ink jet recording device structure such as Fig. 7 of using can keep identical temperature, and obtain and use the essentially identical performance of ink jet recording device of structure shown in Figure 6.In this case, compare, can confirm the total energy consumption decline 0.5-1kW of this system with using other heater.

In next step, use ink jet recording device 1 shown in Figure 2, at the enterprising line item of ink-jet unglazed finish, in order that the performance of test liquid printing ink (2).Being equipped with in the ink jet recording device that uses can be with 1m ³/ min flow blows the air assembly that blows with air.

As a result, confirmed that liquid ink (2) is at 500mJ/cm ²Exposure energy under heating simultaneously, can cured printing ink layer to F level pencil hardness, the curing performance when obtaining to be substantially equal to use warm-up mill.In this case, change the temperature rising that slicken solder is measured data board with thermocolour, the temperature of measuring data board has risen to 80 ℃.Compare with using other heater, confirmed the about 0.5-1kW of total energy consumption decline of this system.

Next, use ink jet recording device 1 shown in Figure 3, at the enterprising line item of ink-jet unglazed finish, in order that the performance of test liquid printing ink (2).Being equipped with in the ink jet recording device that uses can be with 1m ³/ min flow blows the air assembly that blows with air.

As a result, susceptible of proof liquid ink (2) at 540mJ/cm ²Exposure energy under heating simultaneously, can cured printing ink layer to F level pencil hardness, the curing performance when obtaining to be substantially equal to use warm-up mill.In this case, change the temperature rising that slicken solder is measured data board with thermocolour, the temperature of measuring data board has risen to 80 ℃.Compare with using other heater, confirmed the about 0.5-1kW of total energy consumption decline of this system.

Also use ink jet recording device shown in Figure 41, at the enterprising line item of OHP paper.In the ink jet recording device that uses, stop the operation of heater 6, be that the common ultrahigh pressure mercury lamp of 230W is removed structure that cold mirror constitutes as light source from power output.Also be provided with the aluminium reflecting plate, data board is directly heated by the infrared ray of light emitted.

As a result, confirmed that liquid ink (2) is at 480mJ/cm ²Exposure energy under heating simultaneously, make ink lay be cured to F level pencil hardness, obtain the curing performance when being substantially equal to use warm-up mill.In this case, change the temperature rising that slicken solder is measured data board with thermocolour, the temperature of measuring data board has risen to 120 ℃.Compare with using other heater, confirmed the about 0.5-1kW of total energy consumption decline of this system.

In the next step, use ink jet recording device 1, the performance of test liquid printing ink (2) to (4), (6) and (8) to (13) by structure shown in Figure 10.In this case, the container of admitting the recording medium 2 of printing ink image transfer on it is housed in the ink jet recording device 1 of use.Use common glazed paper as recording medium 2, power output is that the ultrahigh pressure mercury lamp of 230W is used as light source 5.Pressure and temperature in the transfer step is set at 10kg/cm respectively ²With 120 ℃.Recording medium is contained in the container after the transfer step, keeps 3 minutes at 80 ℃.As a result, the variation not after transfer step of the image quality before the transfer step, this just shows the transfer that reaches good in all cases.Also find, under the ink jet recording device situation of using structure shown in Figure 11, also obtained essentially identical transfer performance.

On the other hand, according to having prepared relatively printing ink with the identical mode of printing ink (1) to (7), difference is, uses the epoxide of the relatively low aromatic hydrocarbons novolaks series of the plasticity of 40 weight % such as Ep14 and the 60 weight % Ep8 as reaction dissolvent.

Use is made relatively printing ink according to the ink jet recording device 1 of structure shown in Figure 10, and is same, each compared printing ink shift test.Use common glazed paper as recording medium 2, control exposure energy, make light with 200mJ/cm by the output of regulating light source 5 ²Irradiation energy irradiation recording medium 2, the ink lay toughness that makes basic curing.After the step of exposure, at 10kg/cm ²Pressure descends but does not apply heat to shift test, and the result can not shift uniformly.Also use the colored ink with identical photosensitive composition to print, only pigment is changed into Y, C and M.Find that transfer performance is different with color, causes reaching uniform transfer.

Then, use solid ink (liquid ink (22)) to print test continuously.What use in this test is the solid inkjet printing machine that Hewlett-Packard Inc. makes.Find nozzle just obstruction in 30 minutes behind the beginning printing operation, can not continue printing operation.

Equally, use the ink jet recording device of structure shown in Fig. 1,6,10 or 11, each liquid ink (1) to (20) is carried out continuous printing test.Discovery begins after the printing operation even problem did not take place in 500 hours yet.

Liquid ink (2) to (11), (12) and (13) are contained in the print head 5, use ink jet recording device 1, carry out the colored printing performance test by structure shown in Figure 9.The air that the structure of the ink jet recording device that uses in this test should make cooling transfer of all kinds back light source use purges facing to paper.Use the OHP transparent membrane as recording medium 2, power output is the light source 5 of the ultrahigh pressure mercury lamp of 230W as each test.Recording medium is heated to 80 ℃, and air is with about 1m ³The flow of/min purges facing to recording medium, to prevent that the printing ink image from being disturbed.As a result, find that the printing ink mixing of printing back causes the image quality variation, can carry out printing ink satisfactorily and shift.And, in order to probe into the effect that the cooling air produces, cover the cooling air that is used for each light source with the window material, print, do not add thermal recording media.Use the recording medium after the hot plate heating is printed, to concentrate the cured printing ink layer, the result produces " variegated " phenomenon, the i.e. irregular mixing of shades of colour.In other words confirmed that image becomes inhomogeneous.

Example I-2

By the mixed proportion that table 4 is listed, mix the sour polymeric compounds of energy given below (and resin) Ep21-Ep38, prepared composition aa-ap.

Dotted line representative herein

2-5 carbon atom

Table 4

Composition	Compound (weight %)			Liquid ink
					aa	Ep21(87.5)	EP11(12.5)		(41)
ab	Ep22(87.5)	Ep11(12.5)		(42)
					ac	Ep3(50)	Ep23(50)		(43)
ad	Ep3(50)	Ep24(50)		(44)
					ae	Ep3(90)	Ep27(10)		(45)
af	Ep3(50)	Ep26(50)		(46)
					ag	Ep3(40)	Ep25(30)	Ep28(30)	(47)
ah	Ep3(35)	Ep28(35)	Ep29(30)	(48)
					ai	Ep3(50)	Ep30(40)	Ep29(20)	(49)
aj	Ep3(40)	Ep28(60)		(50)
					ak	Ep3(40)	Ep31(40)	Ep32(30)	(51)
al	Ep3(40)	Ep33(40)	Ep34(30)	(52)
					am	Ep3(40)	Ep32(40)	Ep37(30)	(53)
an	Ep3(40)	Ep26(40)	Ep36(30)	(54)
					ao	Ep3(40)	Ep32(40)	Ep35(30)	(55)
ap	Ep3(40)	Ep37(30)	Ep38(30)	(56)

In each composition aa to ap, add 5 weight % carbon blacks as pigment and 8 weight %UVACURE 1591 as photic acid producing agent, use the coating shaking machine that each mixture that makes was carried out dispersion treatment 24 hours.Use the mixture after 5 microns PTEF filter filters dispersion treatment, obtain liquid ink (41) to (56).

Carbon black is crumbed with the serial dispersant of acrylic resin in advance and is prepared the material of crumbing, the material of crumbing that makes is added in the composition together with 200ppm non-ionic surface active agent (Sumitomo 3M Inc. manufacturing) and Ajisper (trade name of Ajinomoto FineTechnology Inc. can be buied).

In the next step, use the ink jet recording device 1 of Fig. 1 or structure shown in Figure 7, each liquid ink (41) to (54) is made a service test.Common glazed paper is as recording medium 2, and power output is that the ultrahigh pressure mercury lamp of 230W is used as light source 5.

Measure the ink lay pencil hardness and the printing quality of liquid ink (41) to (56).Table 5 is listed exposure energy and test result.

Table 5

Liquid ink	Exposure energy MJ/cm 2	Pencil hardness				Printing quality etc.
							After the exposure at once	Container	Room temperature leaves standstill	Hot-rolling
		(41)	450	2B	F						F	F	Well
(42)	450					2B	F	F	F	Well
		(43)	500	2B	HB						F	F	Well
(44)	540					2B	B	F	F	Well
		(45)	450	2B	HB						HB	HB
(46)	350					B	H	H	H	Good especially
		(47)	280	B	H						H	H	Good especially
(48)	290					B	H	H	2H	Printed layers shows solvent resistance
		(49)	350	B	H						H	H	Printed layers shows solvent resistance
(50)	300					B	H	H	2H	Printed layers shows solvent resistance
		(51)	300	B	F						F	F	Printed layers shows solvent resistance
(52)	290					B	H	H	H	Printed layers shows solvent resistance
		(53)	280	B	H						H	2H	Printed layers shows solvent resistance
(54)	350					2B or littler	HB	HB	HB	High volatile volatile and fuzzy
		(55)	320	B	H						H	2H	The typographical display solvent resistance
(56)	250					B	2H	H	3H	The typographical display solvent resistance

Pencil hardness in the table 5 is meant the measured value of ink lay under below the condition.

After the exposure at once: exposure back ink lay state at once.

Container: the ink lay that uses printing machine shown in Figure 7 to form.After the exposure, ink lay kept 3 minutes in 80 ℃ in this container.

Leave standstill under the room temperature: after the exposure, ink lay left standstill 8 hours in room temperature (25 ℃).

Hot-rolling: after the exposure, with the hot-rolling heating ink lay that is heated to 160 ℃.

Under the situation of using liquid ink (48) to (53), (55) and (56), also can the cured printing ink layer under low exposure energy, the photosensitivity that reaches is about 3-8 times that uses liquid ink (21) situation.Use under the situation of liquid ink (48) to (53), (55) and (56), do not stay smell on the printed matter surface, do not observe the intrinsic resinous luster of photosensitive ink, this has just illustrated that printing quality is good.

Specifically be that the liquid ink (46) with epoxide Ep26 of cyclo-aliphatic structure and aliphatic skeleton has high photosensitivity, and curing performance is good.Find that also general its curing performance of composition that contains oxetanes or vinyl ethers is good.

Find, contain the oxetanes of aromatic hydrocarbons skeleton or have under the situation of liquid ink (48) to (53), (55) and (56) of the compound of vinyl ethers skeleton that printed matter can anti-alcohols solvent, and has improved hardness in use.

On the other hand, commercially available contain the printing ink that vinyl ethers has aliphatic skeleton, it has said about liquid ink (54) in front and has been, and finds that its photosensitivity is lower and contain a large amount of volatile components, can cause the printing ink image diffusion.

Example I-3

To comprise and be crushed to Co-γ-Fe that particle diameter is 500nm ₂O ₃Powder, the acrylic acid dispersion liquid as dispersant, the amphoteric resin that is used as the Electrostatic Treatment agent and the mixing of trace metal soap are mediated, afterwards, use the coating shaking machine that kneaded material is dispersed in the epoxide (Ep2), wherein kneaded material is 5 weight % with respect to the content of epoxide (Ep2).The PAG5 that also adds 8 weight % of epoxide weight is used as photic acid producing agent, uses 5 microns PTEF filter to filter the mixture that produces, and obtains function ink composite 1.

The function ink composite that obtains is ejected on the absorbing medium, subsequently with 500mJ/cm ²Exposure energy allow the exposure of this absorbing medium, 100 ℃ of heating afterwards 3 minutes.The result forms magnetic pattern on medium.Magnetic pattern with head scanning forms detects the signal corresponding to visual thickness.

Then, will be as the fine powder of comprising of pigment silver-colored thickener and nickel powder, use sand mill further to pulverize it, and with the dispersant adsorption of polyester series at fine powder pulverized powder particle surface.Use the coating shaking machine, the pressed powder that will deposit this solution acquisition with the amount based on epoxide (Ep1) weight 5% disperses.The PAG5 that also adds based on epoxide 8 weight % is used as photic acid producing agent, and the PTEF filter that re-uses 5 microns filters the mixture that produces, and obtains function ink composite 2.

The function ink composite that obtains is ejected on the absorbing medium, subsequently with 700mJ/cm ²Exposure energy will allow the exposure of this absorbing medium, 100 ℃ of heating afterwards 5 minutes are again in 150 ℃ of these absorbing mediums of compression 30 seconds.The result forms conductive pattern on medium.The conductive pattern that measure to form with a test instrument is that resistance in 100 microns the image is about 100m Ω/cm at width.Equally, use filler powder (SiO ₂) formed insulating pattern.

Example I-4

Shown in previous table 1, epoxy composite b1 contains epoxide Ep3 and epoxide Ep11.The relation of the ratio (%) of epoxide Ep11 and Ep3 comprises the situation that adds the photic acid producing agent of 8 weight % among curve demonstration viscosity among Figure 12 and the epoxy composite b1.In the curve of Figure 12, the ratio of epoxide Ep11 is plotted on the abscissa, and viscosity is plotted on the ordinate.As shown in Figure 12, when viscosity was painted on the log scale, above-mentioned relation linearly.Less than 40% situation, viscosity can not be sprayed this printing ink by the service recorder head greater than 50mPasec in epoxide Ep3 addition.

Also find, to containing the composition of epoxide Ep3 and epoxide Ep11, below shown in equation set up, when from record head satisfactorily during ink jet, the inherent viscosity η t of room temperature is in the 3-30mPasec scope:

ηt＝exp(x1·ln(η1)+x2·ln(η2)+x3·ln(η3)+...+xn·ln(ηn)) (1)

Use epoxide (Ep1) to (Ep9), (Ep10), (Ep11) and any combination (Ep12), measured the viscosity of many points.Under these situations, find that above-mentioned equation sets up, from record head satisfactorily ink jet the time, the inherent viscosity η t of room temperature is in the 3-30mPasec scope.

Example I-5

The ratio of compound (Ep3) and compound (Ep26) in the composition that change table 4 is listed " af ", the result, viscosity is not more than 20mPasec under each situation.This shows, equation (1) in the composition that contains compound (Ep3) and compound (Ep26) is also set up, and from record head satisfactorily during ink jet, the inherent viscosity η t of room temperature is in the 3-30mPasec scope.

Change the ratio of compound (Ep26), prepared ten kinds of compositions.The carbon black that adds 5 weight % in each composition is as pigment, and the PAG5 of 8 weight % uses the coating shaking machine as photic acid producing agent, and the composition that makes is carried out 24 hours dispersion treatment.Use 5 microns PTFE filter, the mixture after the filtration dispersion treatment obtains liquid ink.

In said process, mediate the dispersant of carbon black and acrylic resin series in advance, prepare the material of crumbing, the material of crumbing that makes is added in the said composition together with 200ppm non-ionic surface active agent (Sumitomo 3M Inc. manufacturing) and Ajisper (trade name is made by Ajinomoto Fine Technology Inc.).

Using the ink jet recording device of structure shown in Figure 8, this liquid ink is made a service test, specifically is to measure pencil hardness and the image quality that solidifies image.Table 6 is listed the different proportion and the measurement result of compound (Ep26).

Table 6

Ep26 ratio (%)	10	20	30	40	50	60	70	80	90	100
											Pencil hardness	F	F	H	H	H	H	F	HB	B	2B
Image	Fuzzy	Fuzzy	Well	Good especially	Good especially	Good especially	Well	Not good	Not good	Not good

Use common glazed paper as recording medium 2, the light hammer lamp of being made by Fusion UV System Inc. (lighthammer lamp) is used as light source 5.Also use the microwave heating ceramic material as heating board 18.Found that this glazed paper is with 350mJ/cm ²Photosensitivity sensitization, the photosensitivity of this photosensitivity liquid ink (46) during with the ink jet recording device 1 that uses structure shown in Figure 1 is basic identical.Find that also as shown in table 6, when at compound (Ep26) and (Ep3) content was at least 30 weight % separately, performance was obviously improved.To compound (Ep3), (Ep1), (Ep6), (Ep21) and (Ep22) and compound (Ep23), (Ep24), (Ep25) and mixture (Ep26), also observe this particular tendency.

Example I-6

Cycloaliphatic compounds (Ep3) remains unchanged (equating) with the ratio of cycloaliphatic compounds (Ep28) in the composition shown in the table 4 " ah ", changes the ratio of compound (Ep3+Ep28) and compound (Ep29).

The ratio that changes compound (Ep29) has prepared five kinds of compositions.The carbon black that adds 5 weight % in each composition that makes is as pigment, and the PAG5 of 8 weight % uses the coating shaking machine as photic acid producing agent, and the composition that makes is carried out 24 hours dispersion treatment.Use 5 microns PTFE filter, the mixture after the filtration dispersion treatment obtains liquid ink.

In said process, mediate the dispersant of carbon black and acrylic resin series in advance, prepare the material of crumbing, the material of crumbing that makes is added in these compositions together with 200ppm non-ionic surface active agent (Sumitomo 3M Inc. manufacturing) and Ajisper (trade name is made by Ajinomoto Fine Technology Inc.).

Use the ink jet recording device of structure shown in Figure 1, these five kinds of liquid inks are made a service test.Use common glazed paper as recording medium 2, in container, heated 5 minutes after the step of exposure in 60 ℃.The ultrahigh pressure mercury lamp that is output as 230W is as light source 5.Table 7 is listed in the ink viscosity under different compounds (Ep29) the ratio situation, the photosensitivity of solidifying image and the jet performance of printing ink.Can be well understood to by table 7, fragrant oxetane compound content is poor above the jet performance of the oxygen heterocycle butane printing ink of 40 weight %.

Table 7

Ep29 ratio (%)	10	20	30	40	50
						Viscosity (mPas)	12.0	16.4	22	28.7	37.8
Photosensitivity (mJ/cm 2)	390	350	320	300	280
						Performance and injection	Photosensitivity is low	Well	Good especially	Image slightly disturbs	Stop up in the injection, no thermoplasticity, thereby can't shift

Can confirm that the equation that provides previously in this case (1) is also set up.Can be under record head injection situation satisfactorily at printing ink, its room temperature inherent viscosity η t is in the 3-30mPasec scope.

Example I-7

Change the ratio of compound (Ep3) and compound (Ep28).

Change compound (Ep3) ratio ten kinds of compositions of preparation.The carbon black that adds 5 weight % in each composition that makes is as pigment, and the PAG5 of 8 weight % uses the coating shaking machine as photic acid producing agent, and the composition that makes is carried out 24 hours dispersion treatment.Use 5 microns PTFE filter, the mixture after the filtration dispersion treatment obtains liquid ink.

In said process, mediate the dispersant of carbon black and acrylic resin series in advance, prepare the material of crumbing, the material of crumbing that makes is added in these compositions together with 200ppm non-ionic surface active agent (Sumitomo 3M Inc. manufacturing) and Ajisper (trade name is made by Ajinomoto Fine Technology Inc.).

Use the ink jet recording device of structure shown in Figure 1, each liquid ink is made a service test.Use common glazed paper as recording medium 2, in container, heated 5 minutes after the step of exposure in 60 ℃.Use power output as the ultrahigh pressure mercury lamp of 230W as light source.Table 8 is listed under different compounds (Ep3) the ratio situation, solidifies the hardness of image and the result of photosensitivity and jet performance.

Can be well understood to by table 7, if the ratio of compound (Ep3) surpasses 30 weight % or is not less than 30 weight %, solvent resistance can descend, and curing performance also can descend.

Table 8

Ep3 ratio (%)	10	20	30	40	50	60	70	80	90	100
											Pencil hardness	B	B	HB	F	H	H	F	F	F	F(HB)
Solvent resistance	Good	Good	Good	Well	Well	Difference	Very poor	Very poor	Very poor	Very poor

Change compound (Ep3), (Ep28) and mixing ratio (Ep29), test a series of samples.Find, be not more than 40 weight portions at aromatic hydrocarbons oxetane compound content, there is the epoxide content of cyclic aliphatic skeleton to be not more than 60 weight portions, the total addition of compound with oxetanes skeleton is not less than 40 weight portions, the total addition that had not only had the cyclic aliphatic skeleton but also had a compound of aromatics skeleton is not less than the situation of 30 weight portions, can obtain gratifying solvent resistance, keep good heat transmission characteristic ability, be not less than the pencil hardness of HB and the ink characteristics of jet performance.

Example I-8

The ink composite for preparing from the foregoing description is respectively got 4 grams and is contained in the Petri dish of internal diameter 5.9cm and diameter 6cm, the evaporation rate when the mensuration culture dish is heated to 80 ℃ under environmental pressure.Find that composition (6), (8), (41), (43), (44), (46)-(53), (55) and (56) evaporation rate separately are no more than 0.2mg/cm ²Min.Composition in the time of 5 minutes, does not smell tangible smell 65 ℃ of heating after the step of exposure, therefore, possesses good performance.

Example I-9

Preparation method according to liquid ink (46) prepares various liquid inks, and difference is, changes the addition of photic acid producing agent in the composition " af " of table 4 into 1 weight %, 2 weight %, 4 weight %, 6 weight % and 10 weight % respectively.Find, the initial viscosity of each liquid ink all is about 17mPa/s.

Use the ink jet recording device 1 of structure shown in Figure 1, each liquid ink is carried out performance test.Table 9 is listed in photosensitivity and the spray regime after the accelerated test of carrying out for 1 week under 60 ℃ of heating and the photic acid producing agent additional proportion (the weight % of clean addition does not comprise solvent):

Table 9

Photic acid producing agent additional proportion	1	2	4	6	8	10
							Photosensitivity (Mj/cm 2)	790	400	360	350	350	350
Viscosity * (mPas)	20	23	29	35	50	83
							Jet power	Well	Well	Well	Well	Hardly may	Impossible
The Ni corrosion	Do not have	Do not have	The trace corrosion	A small amount of corrosion	Corrosion	Macro-corrosion

*: 60 ℃ store 1 month after

Photosensitivity was lower when as shown in Table 9, photic acid producing agent concentration was 1 weight %.Can find out that also when photic acid producing agent concentration was increased to 10 weight %, viscosity significantly improved.Table 9 data show that also the Ni metal that forms pipe or electrode is immersed in and has corrosion to take place in the printing ink.If photic acid producing agent addition is not less than 8 weight %, find that etching extent increases.

Example II

The formulation epoxy composite a2 to g2 that lists according to table 10.The epoxide that uses in the epoxide that uses among this embodiment and the example I is identical.

Table 10

Epoxy composite	Epoxide (weight %)
					a2	Ep3(87.5)	Ep10(12.5)
b2	Ep3(50)	Ep26(50)
					c2	Ep3(60)	Ep29(40)
d2	Ep3(40)	Ep28(40)	Ep31(20)
					e2	Ep3(50)	Ep32(25)	Ep33(25)
f2	Ep3(40)	Ep37(30)	Ep38(30)
					g2	Ep3(40)	Ep26(20)	Ep31(30)	Ep35(10)

Prescription according to table 11 is listed adds pigment, photic acid producing agent and viscosity stabiliser in each epoxy composite a2 to g2, use the coating shaking machine, and the composition that makes is carried out 24 hours dispersion treatment.Use 5 microns PTFE filter, the mixture after the filtration dispersion treatment obtains liquid ink (61) to (82).

In said process, use carbon black, C.I. pigment Yellow 12 8, C.I. pigment blue 15 and C.I. pigment red 123 respectively as black pigment, yellow uitramarine, cyano group pigment and magenta pigment.These pigment are mediated with the serial dispersant of acrylic resin in advance separately and are prepared the material of crumbing, the material of crumbing that makes is added in the epoxy composite together with 200ppm non-ionic surface active agent (Sumitomo 3M Inc. manufacturing) and Ajisper (trade name is made by Ajinomoto Fine TechnologyInc.).

Foregoing compound is as photic acid producing agent PAG1 to PAG5.Also add by the alkali compounds of Formula B S1 to BS7 representative or alkalogenic compound as viscosity stabiliser, its addition is that the mole % of benchmark represents with the clean amount of photic acid producing agent, as the 1 weight % of 8.3 moles of % corresponding to BS3 and PAG5 combination.

Table 11

Liquid ink	Epoxide	Pigment (weight %)	Acid agent solution (weight %)	Viscosity stabiliser (mole %)
					61	a2	BL(5％)	PAG5(8％)	BS1(8.3％)
62	a2	BL(5％)	PAG5(8％)	BS2(8.3％)
					63	a2	BL(5％)	PAG5(8％)	BS3(8.3％)
64	a2	BL(5％)	PAG5(8％)	BS4(8.3％)
					65	a2	BL(5％)	PAG5(8％)	BS5(8.3％)
66	a2	BL(5％)	PAG5(8％)	BS6(8.3％)
					67	a2	BL(5％)	PAG5(8％)	BS7(8.3％)
68	b2	BL(5％)	PAG5(8％)	BS3(8.3％)
					69	c2	BL(5％)	PAG5(8％)	BS1(8.3％)
70	d2	BL(5％)	PAG5(8％)	BS1(8.3％)
					71	e2	BL(5％)	PAG5(8％)	BS3(8.3％)
72	f2	BL(5％)	PAG5(8％)	BS3(8.3％)
					73	g2	BL(5％)	PAG5(8％)	BS1(8.3％)
74	a2	Y(5％)	PAG5(8％)	BS5(8.3％)
					75	a2	C(5％)	PAG5(8％)	BS5(8.3％)
76	a2	M(5％)	PAG5(8％)	BS158.3％)
					77	b2	BL(5％)	PAG1(8％)	BS7(8.3％)
78	b2	BL(5％)	PAG2(8％)	BS7(8.3％)
					79	b2	BL(5％)	PAG3(8％)	BS7(8.3％)
80	b2	BL(5％)	PAG4(8％)	BS7(8.3％)
					81	a2	-	PAG5(8％)	-
82	a2	BL(5％)	PAG5(8％)	-

The printing ink that has also prepared wherein unmixed pigment and viscosity stabiliser obtains liquid ink (81) and (82).

Table 12 is listed the initial viscosity of each liquid ink shown in the table 11 and is at room temperature left standstill viscosity after 6 months.

Table 12

Liquid ink	Viscosity (mPas)		Other performance variation
				Initially	After leaving standstill 6 months under the room temperature
	61	19.4				23.4	Coating is slightly inhomogeneous
62			19.4	21.4
	63	19.4				29.9
64			19.4	21.3
	65	19.4				19.4
66			19.4	21.6
	67	19.4				19.8
68			20.7	21.5
	69	24.0				24.9
70			12.6	13.0
	71	6.1				6.8
72			7.7	7.5
	73	6.1				6.8
74			18.3	17.9
	75	20.4				21.7
76			19.8	21.2
	77	18.8				19.5
78			17.6	18.8
	79	20.2				25.5
80			19.5	19.7
	81	14.4				33.64
82			19.3	103.1	Coating is inhomogeneous

As shown in table 12, unmixed have the liquid ink (81) of viscosity stabiliser and the viscosity of (82) all obviously to increase.The viscosity that particularly contains the liquid ink (81) of carbon black serial pigment significantly increases.

In the step under connecing, use the ink jet recording device 1 of Fig. 6, each liquid ink (61) to (80) and (82) are carried out the performance comparative test, to compare initial performance and the performance after 6 months.Test adopts common glazed paper as recording medium 2, and power output is that the high-pressure sodium lamp of 230W is used as light source 5.Measure the ink lay pencil hardness (after the step of exposure, ink lay in container in 80 ℃ of hardness after keeping 3 minutes) and the printing quality of each liquid ink (61) to (80).Table 13 has been listed different light exposures and test result.

Table 13

Liquid ink	Expose back 80 ℃ 3 minutes		After 6 months		Printing quality etc.
						Light exposure (mJ/cm 2)	Pencil hardness	Light exposure (mJ/cm 2)	Pencil hardness
	61	600	F	650	HB						Well
62						550	F	550	F	Well
	63	550	F	550	F						Well
64						530	F	530	F	Well
	65	480	F	480	F						Well
66						450	F	460	HB	Well
	67	480	F	480	F						Well
68						390	H	390	H	Well
	69	290	H	290	H						Well
70						310	H	310	H	Well
	71	280	2H	280	2H						Well
72						320	H	320	H	Well
	73	320	H	320	H						Slightly inhomogeneous
74						640	F	650	F	Well
	75	550	F	540	F						Well
76						520	F	550	F	Well
	77	350	F	350	F						Well
78						780	F	780	F	Well
	79	800	F	800	F						Well
80						1000	F	1000	F	Well
	82	450	F	-	-						Can not spray

As shown in table 13, the viscosity of liquid ink obviously improves, so that can not be from record head atomizing of liquids printing ink.And contain alkali compounds or produce alkaline agent each liquid ink (61) to (80) as viscosity stabiliser, its viscosity is obviously stable.

Use liquid ink (61) to (80), with regard to energy cured printing ink layer, the stability of printing ink significantly improves with relatively little light exposure.Make with resolvent alkali compounds BS6 or BS7 under the light irradiation, photosensitivity is high especially, and therefore, ink performance is good.

Also tested the corrosivity when being used to form pipe or the nickel metal of chieftain's parts and contacting with liquid ink.Find that the nickel metal is not corroded fully.On the other hand, and with each liquid ink (81) that does not contain viscosity stabiliser or (82) when contacting the nickel metal find to be corroded, illustrate that viscosity stabiliser also has the function of resist.

Then, the preparation other is formed and the essentially identical ink composite of liquid ink (68), and difference is to change the addition (based on the mole % of photic acid producing agent) as the alkali compounds BS3 of viscosity stabiliser.Measure the pencil hardness of these ink composites and viscosity increment rate after 6 months.Table 14 is listed ratio and the test result that changes compd B S3.

Table 14

BS3 ratio (mole %)	1	2	7	14	28	56	70	75	100
										Pencil hardness	F(H)	F	F(HB)	HB(F)	B	＜2B	-	-	-
The viscosity increment rate	505 (initial values 5 times)	34	7	5	3	2	3	1	2

As shown in table 14, find to add when being the viscosity stabiliser of 1 mole of % of benchmark with photic acid producing agent, printing ink almost can not be stablized.Find that also when if the viscosity stabiliser addition surpasses about 28 moles of %, the curing performance of printing ink descends.

As mentioned above, according to the present invention, can provide a class high performance liquid ink, this liquid ink does not need organic solvent and large-scale exposure system to obtain high printing quality.And, according to the present invention, can provide the ink jet recording device that can use this kind liquid ink to make printed matter.

Those skilled in the art can understand other advantages of the present invention and modification.Therefore, the present invention more broad aspect be not subjected to the restriction of detail described here and representative embodiment.Therefore, in the spirit and scope of the present invention that do not depart from appended claims and its content qualification of equal value, can carry out various modifications to the present invention.

Claims (8)

1. ink jet recording device that uses liquid ink on recording medium, to form the printing ink image, described equipment comprises:

Shift the transfering part (3) of recording medium (2);

Be contained in the inkjet type record head (4) of transfering part (3) top, described inkjet type record head is injected in liquid ink on the recording medium, forms ink lay on recording medium;

Light source (5) with the described ink lay of light irradiation; And

Heat the heating element heater (6) of described ink lay;

It is characterized in that described light source is launched infrared ray simultaneously radiative, and have the reflecting plate of reflected infrared ray and/or transmit ultrared transmission window; Described liquid ink is included in the solvent of acidic photic acid producing agent, colouring component and at least a polymerization in the presence of acid under the light irradiation, described in the presence of acid the theobromine polymerizable compound of polymerization have cyclic aliphatic skeleton and/or aliphatic skeleton, its viscosity under room temperature and environmental pressure is not more than 50mPas, and boiling point is not less than 150 ℃.

2. ink jet recording device as claimed in claim 1 is characterized in that, described heating element heater (6) is the heater that separates installation with light source (5).

3. ink jet recording device as claimed in claim 1, it is characterized in that, described ink jet recording device also comprises the gaseous material passage (9) of gaseous matter through light source, and to obtain the gaseous material through heat exchange, light source and the set of gaseous state substance channel form heating element heater.

4. ink jet recording device as claimed in claim 3, it is characterized in that, described equipment also comprises the heating mantles (10) that is connected with light source (5), injected the gaseous material after heat exchange in this heating mantles, and this heating mantles has recording medium, and described recording medium comprises the ink lay of transferring on it behind light irradiation.

5. ink jet recording device as claimed in claim 1 is characterized in that, described heating element heater comprises light source (5) and reflecting plate and/or transmits window.

6. ink jet recording device as claimed in claim 2 is characterized in that, described equipment also comprises the container (7) that holds recording medium behind a plurality of smooth irradiation, heats with heating element heater in this container.

7. ink jet recording device as claimed in claim 1 is characterized in that, described light source (5) is launched light under the frequency electromagnetic waves effect;

Described equipment also comprises to light source (5) provides the high frequency generating apparatus (14) of frequency electromagnetic waves, the electromagnetic shield (15) of ambient light source (5) periphery, at least be formed with a hole on its surface facing to transfering part, be arranged in the heat production medium (16) on transfering part (3) back side, it produces heat under the irradiation of frequency electromagnetic waves;

Heating element heater comprises launches light and electromagnetic light source (5), high-frequency electromagnetic wave generating device (14) and heat production medium (16) simultaneously.

8. ink jet recording device as claimed in claim 1, it is characterized in that, be arranged with a plurality of inkjet type record heads (4a, 4b, 4c, 4d), they spray the multiple inks that color differs from one another, form the ink lay of different colours, after forming a single ink lay each time, carry out light irradiation and/or heating.

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