CN101130648A - Photocurable ink set, and printing method, printing apparatus and printed matter each using the same - Google Patents
Photocurable ink set, and printing method, printing apparatus and printed matter each using the same Download PDFInfo
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- CN101130648A CN101130648A CN 200710141751 CN200710141751A CN101130648A CN 101130648 A CN101130648 A CN 101130648A CN 200710141751 CN200710141751 CN 200710141751 CN 200710141751 A CN200710141751 A CN 200710141751A CN 101130648 A CN101130648 A CN 101130648A
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Abstract
The present invention provides a photocurable ink set comprising a chromatic ink containing no photoradical polymerization initiator and an achromatic ink containing at least one or more photoradical polymerization initiators. Also disclosed are a printing method, a printing apparatus and a printed matter, each using the ink set.
Description
Technical field
The invention provides light-cured type ink group, the printing process of using this ink group, printing device and print that a kind of utilization is cured, say that in more detail it is outstanding and form light-cured type ink group, the printing process of using this ink group, printing device and the print of high meticulous image to relate to the image solidified nature.
Background technology
Ink jet recording method is the droplet of ink group thing to be circled in the air and printing process that it is printed attached to recording mediums such as paper.This ink jet recording method is characterised in that, can the high speed printing high-resolution, high-quality image.At the composition for ink that the ink jet recording method clock uses, be main component with the aqueous solvent, contain coloring components therein usually and be the wetting agents such as glycerine of purpose to prevent to stop up.
On the other hand, when the paper of the kind that is difficult to soak at aqueous ink composition, be coated paper, printed book paper, dry goods, perhaps unsoaked metal, plastic or other material, for example by on the recording mediums such as the plate of resin manufacture such as phenol, trimeric cyanamide, vinylchlorid, vinylformic acid, polycarbonate, film during lettering, it is stable and can anchor at composition on the recording medium to require to contain in composition for ink coloured material.
For such requirement, disclose and contain the light-cured type ink for ink-jet print (for example, with reference to patent documentation 1) that coloured material, light curing agent (free-radical polymerised compound), optical free radical (polymerization starter) etc. form.Utilize this ink, can prevent the infiltration of ink, improve image quality to recording medium.
In addition, in order to prevent the infiltration of ink, carry out the lettering of high image quality, developed method (patent documentation 2) to recording medium ejection composition for ink and two kinds of liquid of reaction solution, the composition for ink that soon before ink head ejection ink, is containing coloured material and polymerizable compound, mix the ink jet recording method (patent documentation 3) of the reaction solution that contains Photoepolymerizationinitiater initiater, on recording materials, spray the ink jet recording method (patent documentation 4) of the light-cured type ink that contains coloured material etc. after the poor light-cured type ink of ejection look material.
Patent documentation 1: No. the 5623001st, United States Patent (USP)
Patent documentation 2: the spy opens 2000-158793 number
Patent documentation 3: the spy opens 2003-89261 number
Patent documentation 4: the spy opens 2005-96254 number
In two liquid hybrid optical curing inks, when mixing two kinds of liquid, look material concentration reaches 1/2, has the insufficient problem of depth of shade.Particularly bigger with regard to influence in the achromaticity ink, be difficult to avoid the identification reduction in the black ink, the disguise in the white ink to reduce.
In addition, estimate that look material concentration reaches 1/2, the look material concentration that improves in these composition for ink is improved the required energy of photocuring easily, and it is bad to cause curing.The pigment carbon black that particularly contains in the black ink, because strong absorption visible light, UV-light, so the increase of pigment concentration causes the increase of irradiation energy, improve the load of curing process, the result causes maximization, the increase of productive temp time (tacttime) of device.
In addition, when Photoepolymerizationinitiater initiater after a little while, radical polymerization can fully not carried out, and can fully not solidify, and has unreacted monomer residue.And then, even if, improve under the situation of the concentration in the composition for ink, storage stability (working lipe) also can occur and reduce estimating that Photoepolymerizationinitiater initiater liquid reaches 1/2 concentration, the polymerization degree of the reactant of Sheng Chenging does not improve in addition and completely solidified not.Infer this be because, monomer reduces with respect to the quantity of the free radical that is produced by Photoepolymerizationinitiater initiater, the radical polymerization product does not grow to polymkeric substance but stays in oligopolymer.Particularly under the situation of color inks, when because the polymerization degree of the difference of color and cured article not simultaneously, exists color seepage or the cohesion of look material etc. to produce the problem of unfavorable condition on the image that forms.
Summary of the invention
Therefore, the present invention overcomes above-mentioned technological deficiency in the past, provides the image solidified nature outstanding and form the light-cured type ink group of high precise image.
The inventor concentrates on studies repeatedly, found that, by adopting following formation, can realize above-mentioned purpose, thereby finish the present invention.
That is, the present invention is as described below.
(1) a kind of light-cured type ink group is characterized in that, contains the color inks that does not contain the optical free radical polymerization starter and contains the achromaticity ink of at least a above optical free radical polymerization starter.
(2) in the light-cured type ink group of (1) record, it is characterized in that the achromaticity ink comprises black ink, white ink, grey chromatic ink, light/dark balance ink and transparent ink (clear ink).
(3) in the light-cured type ink group of (1) or (2) record, it is characterized in that white ink contains hollow resin.
(4) in (1)～(3) in the light-cured type ink group of any record, it is characterized in that, color inks is to be selected from yellow ink, magenta ink, cyan, as their light yellow ink, shallow magenta ink, the pale cyan inks of light ink, as in red ink, green ink, blue ink, orange ink, brown ink and the purple ink of secondary color more than one.
(5) used the printing process of the light-cured type ink group of any record in (1)～(4).
(6) in the printing process of (5) record, it is characterized in that, the achromaticity ink is solidified separately.
(7) in the printing process of (5) record, it is characterized in that, the achromaticity ink is mixed with other achromaticity inks and make its curing.
(8) in (5)～(7), in the printing process of any record, color inks is made its curing by mixing with the achromaticity ink.
(9) used the printing device of the light-cured type ink group of any record in (1)～(4).
(10) print that the light-cured type ink group of any record prints in use (1)～(4).
Embodiment
Below, light-cured type ink group of the present invention is elaborated.Light-cured type ink group of the present invention is characterised in that, contains the color inks that does not contain the optical free radical polymerization starter and contains the achromaticity ink of at least a above optical free radical polymerization starter.
As the optical free radical polymerization starter that in color inks of the present invention and achromaticity ink, uses; be not particularly limited; but preferred alpha-amino group ketone, alpha-alcohol ketone, acyl group phosphine oxygen for example can be enumerated Alpha-hydroxy alkyl phenones, alpha-aminoalkyl benzophenone, monoacyl phosphine oxygen, two acyl group phosphine oxygen.
In addition, can also use can be with the optical free radical polymerization starter of trade(brand)name Irgacure 127,184,2959,369,379,907,1700,1800,1850,1870,819,4265, Darocur 1173, DPO (CIBASPECIALTY CHEMICALS corporate system) acquisition.
The addition of optical free radical polymerization starter is preferably 0.1 weight %～15 weight % in composition for ink, more preferably 0.5 weight %～10 weight %.Under the very few situation of addition, because polymerization velocity is low, the influence of oxygen quenching increases, and becoming, it is bad to solidify.Under the situation of addition surplus, the molecular weight of cured article is low, only obtains the low cured article of weather resistance.
As the optical free radical polymerizable compound that in color inks of the present invention and achromaticity ink, uses, so long as the common material that in the light-cured type ink, uses, just be not particularly limited, single allylic cpd of preferably enumerating, more preferably enumerate allyl ether compound, ethylene glycol monoallyl ether, trimethylolpropane allyl ether, the TriMethylolPropane(TMP) mono allyl ether, allylin, glycidyl allyl ether, pentaerythritol triallyl ether especially preferably contains ethylene glycol monoallyl ether, trimethylolpropane allyl ether and/or N-vinyl compound, preferred especially N-vinyl formamide.
Ethylene glycol monoallyl ether and/or N-vinyl formamide make the free radical polymerization monomer of simple function, in the preservation process, because that unwanted polymeric tendency appears in dark reaction is lower, are suitable for using.
Allyl ether compound such as ethylene glycol monoallyl ether, trimethylolpropane allyl ether particularly is even if the carbon radicals that exists the decomposition by the optical free radical polymerization starter to produce also has polymeric characteristic separately.
When the addition of ethylene glycol monoallyl ether and/or N-vinyl formamide is no more than 20 weight %, the problem of the viscosity of appearance composition for ink, dispersion stabilization, storage stability etc., when its addition is more when surpassing 80 weight %, as the solidified nature of two-component-type photocuring composition for ink, abundant inadequately sometimes by film toughness.The scope of 20 weight %～70 weight % more preferably.
In addition, in color inks of the present invention and achromaticity ink, contain branch-shape polymer sometimes as the optical free radical polymerizable compound.As dendritic polymer, can rough classification as follows become 6 kinds of structures.
I branch-shape polymer (dendrimer)
II wire branch-shape polymer
III dendroid graftomer
IV over-expense chain polymerization thing
V star over-expense chain polymerization thing
The super graftomer of VI
Wherein, the branching index of I～III (DB:degree of branching) is 1, has flawless structure, and relative therewith, IV～VI has the random branched structure that can contain defectiveness.Particularly dendritic polymer is compared with the polymer of normally used linearity, can be in its reactive functional group of outermost high-density centralized configuration, and as functional high molecule material, higher to its expectation.In addition, although over-expense chain polymerization thing is such not as branch-shape polymer, also can import a large amount of reactive functional groups to its outermost, solidified nature is outstanding.
These dendritic polymer are different with in the past linearity polymer or branched polymer, repeat branched structure three-dimensionally, are highly branched structure., compare for this reason, preferably use the polymkeric substance of number-average molecular weight, especially preferably use the polymkeric substance of number-average molecular weight in 2000～50000 scope in 1000～100000 scope with the linearity polymer of same molecular weight.When molecular weight was lower than above-mentioned scope, the photographic fixing image became fragile, and when molecular weight was higher than above-mentioned scope, even if reduce addition, the viscosity height of ink increased in addition, and is from ejection characteristic aspect, impracticable.
In addition, branch-shape polymer that can use in the present invention and over-expense chain polymerization thing preferably have the branch-shape polymer of the functional group that radical polymerization can take place and overspend the chain polymerization thing at outermost.Can be by being in the structure of outermost generation radical polymerization, polyreaction can be carried out fast.
As the example of the polymkeric substance with branch-shape polymer structure, amino amides is that branch-shape polymer can be enumerated disclosed material in No. the 4507466th, United States Patent (USP), No. the 455812nd, United States Patent (USP), No. the 4568737th, United States Patent (USP), No. the 4587329th, United States Patent (USP), No. the 4631337th, United States Patent (USP), No. 4694064 specification sheets of United States Patent (USP); Phenyl ether is that branch-shape polymer can be enumerated disclosed material in No. 5041516 specification sheets of United States Patent (USP), Journal of American Chemistry 112 volumes (nineteen ninety, 7638～7647 pages) etc.About amino amides is branch-shape polymer, and the branch-shape polymer with terminal amino group and carboxylate methyl ester base is being sold as " StarburstTM (PAMAM) " on the market by Aldrich company.In addition, can also make this amino amides is that the terminal amino group of branch-shape polymer and various acrylic acid derivative and methacrylic acid derivative react, and synthetic amino amides with respective ends is a branch-shape polymer, and uses them.
As utilizable acrylic acid derivative and methacrylic acid derivative, can enumerate acrylic or methacrylic acid alkyl esters such as methyl esters, ethyl ester, positive butyl ester, the tert-butyl ester, cyclohexyl, palm ester, stearyl ester, acrylamide, the alkylamide of acrylic or methacrylic acid such as sec.-propyl acid amides, but be not limited to these.
In addition, about phenyl ether is branch-shape polymer, roll up (nineteen ninety at Journal of American Chemistry112,7638～7647 pages) in record various polymkeric substance, for example record: use 3, the 5-dihydroxy-benzyl alcohol, make itself and 3,5-two phenoxy benzyl bromines react, and the benzyl alcohol in synthetic the 2nd generation uses CBr
4With triphenylphosphine its OH base is transformed into after the Br, similarly make itself and 3, the 5-dihydroxy-benzyl alcohol reacts, the benzyl alcohol in synthetic the 2nd generation, synthetic follow-on benzyl alcohol below carries out above-mentioned reaction, the synthetic branch-shape polymer that needs repeatedly.About phenyl ether is the dendroid composition, can replace terminal benzyl ehter bond, replaces terminal with the material with various chemical structures.For example, roll up (nineteen ninety when carrying out Journal of American Chemistry 112,7638～7647 pages) in during branch-shape polymer synthetic of record, as long as use various alkylogens to replace above-mentioned bromotoluene, the phenyl ether that just can obtain having end structure is a branch-shape polymer, and this end structure has suitable alkyl.Other polyamines are that can to use the polyamines shown in the Macromol.Symp.77,21 (1994) be branch-shape polymer and with the derivative of its end group modification to branch-shape polymer.
As over-expense chain polymerization thing, for example can use over-expense chain polyalkylene glycol etc.Over-expense chain polymerization thing uses at an intramolecularly has a kind of reflecting point that is equivalent to the branching part more than 2 and the only monomer of a reflecting point that is equivalent to other kinds of connection portion, the polymkeric substance that obtains thus with synthetic target polymkeric substance of a stage (Macromolecules, 29 volumes (1996), 3831～3838 pages).For example, with a monomeric example, can enumerate 3,5-resorcylic acid derivative as the over-expense linked polymer.If enumerate the Production Example of over-expense linked polymer, can be under nitrogen atmosphere, to heat 3, two ((the 8 '-hydroxyls-3 ' of 5-, 6 '-two oxa-octyl groups) oxygen base) methyl benzoate and diacetate esters dibutyl tin, synthetic poly-[two (triethylene glycol) benzoic ether] as the over-expense linked polymer, wherein said 3, two (the 8 '-hydroxyls-3 ' of 5-, 6 '-two oxa-octyl groups) oxygen base) methyl benzoate is by 1-bromo-8-(tert-butyl diphenyl siloxy-)-3,6-two oxa-octanes and 3, the 5-methyl dihydroxy benzoate obtain 3, two (8 '-(tert-butyl diphenyl siloxy-)-3 ', 6 '-two oxa-octyl groups) the oxygen bases of 5-) hydrolysate of methyl benzoate.
When using 3, during 5-resorcylic acid ester, become hydroxyl because overspend the linked polymer end group, so with respect to this hydroxyl, by using suitable haloalkane, can synthesize over-expense linked polymer with various end groups.
Have the monodisperse polymer of branch-shape polymer structure or overspend linked polymer etc., utilize the chemical structure of main chain and the chemical structure of its end group to arrange its characteristic, but particularly a great difference is arranged because of its characteristic of substituent difference in end group or the chemical structure.Branch-shape polymer with polymerizable group is to carry out chemically modified with the compound with polymerizable group has a compound of basic groups such as amino, substituted-amino, hydroxyl to end end to obtain.
For example, to being that branch-shape polymer Michael addition contains among the polyfunctional compound that (methyl) acrylate based compound of active hydrogen forms to amino, for example addition contains the vinyl compound of isocyanate group and synthesizes.In addition, by making amino is that branch-shape polymer and for example (methyl) vinylformic acid muriate etc. react, can obtain the branch-shape polymer that end has polymerizable group, as the vinyl compound that gives such polymerizable group, can enumerate compound with the alkene unsaturated link(age) that can carry out radical polymerization, as its example, can enumerate vinylformic acid, methacrylic acid, methylene-succinic acid, Ba Dousuan, iso-crotonic acid, unsaturated carboxylic acid such as toxilic acid and their salt etc., various compound described later with the alkene unsaturated link(age) that can carry out radical polymerization.
In the present invention, above-mentioned branch-shape polymer and over-expense linked polymer can only be used alone, and can also also use with the branch-shape polymer and the over-expense linked polymer of other kinds.
Because the legislate height of branch-shape polymer, so the worker ordinal number increases and cost up, but the legislate of over-expense linked polymer is high unlike branch-shape polymer, can synthesize with comparalive ease, so be favourable aspect cost.
In the present invention, as the over-expense linked polymer, use Osaka organic chemistry industry system, " VISCOAT#1000 ", " STAR-501 ".This " VISCOAT#1000 ", " STAR-501 " are to be the over-expense linked polymer that core makes functional group's branching with the Dipentaerythritol, " VISCOAT#1000 " is as diluting monomer, contain glycol diacrylate, viscosity is 273mPas, and functional group's number is 14 (acryls); " STAR-501 " contains dipentaerythritol acrylate as diluting monomer, and viscosity is 210mPas, and functional group's number is 20～99 (acryls).Any all have acryl at outermost, can suitably use.
In color inks of the present invention and achromaticity ink, the scope about the preferred 3 weight % of the addition of above-mentioned dendritic polymer～30 weight % can keep the suitability as two-component-type photocuring composition for ink.The more preferably scope about 5 weight %～25 weight %.If the addition of dendritic polymer is abundant inadequately as the solidified nature of two-component-type photocuring composition for ink less than 3 weight %, if increasing, it surpasses 30 weight %, produce the problem of the viscosity, dispersion stabilization, storage stability etc. of ink sometimes.
As other free-radical polymerised compounds, be not particularly limited, but for example can enumerate monomer (monomer).
Monomer is meant can become the formation of high molecular basic structure unit.In addition, the monomer of Shi Yonging is also referred to as photopolymerization monomer in the present invention, and monofunctional monomer, two functional monomers, polyfunctional monomer are arranged, and can use.The all preferred PII value (Primary Irritation Index, a skin irritation) of any monomer is below 2.
The PII value that can use in the present invention is that monofunctional monomer, two functional monomers and the polyfunctional monomer below 2 is illustrated in the following table 1.
Table 1
| Monofunctional monomer | ||
| The material name | Viscosity (mPas) | P.I.I. |
| Vinylformic acid (2-methyl-2-ethyl-1,3-two oxa-s penta ring-4-yl) methyl esters (MEDOL-10, Osaka organic) | 5.1 | 1.3 |
| Vinylformic acid (2-methyl-2-isobutyl--1,3-two oxa-s penta ring-4-yl) methyl esters (MIBDOL-10, Osaka organic) | 5.3 | 1.0 |
| Vinylformic acid phenoxy ethyl (VISCOAT#192, Osaka organic) | 3.3 | 1.7 |
| Isobornyl acrylate (IBXA, Osaka organic) | 2.6 | 0.6 |
| Methoxyl group diethylene glycol monoacrylate (BLEMMER PME-100, Japanese grease) | 2 | 0.7 |
| Acryloyl morpholine (ACMO, emerging people) | 12 | 0.5 |
| Two functional monomers | ||
| The material name | Viscosity (mPas) | P.I.I. |
| Ethylene glycol dimethacrylate (ラ イ ト エ ス テ Le EG, common prosperity society chemistry) | 3 | 0.6 |
| Diethylene Glycol dimethacrylate (ラ イ ト エ ス テ Le 2EG, common prosperity society chemistry) | 5 | 0.5 |
| Tripropylene glycol diacrylate (synthesize in ア ロ ニ Star Network ス M-220, East Asia) | 12 | 1.6 |
| 1,9-nonanediol diacrylate (VISCOAT#260, Osaka organic) | 21 | 2.0 |
| Polyoxyethylene glycol #400 diacrylate (NK エ ス テ Le A400, Xin Zhong village chemistry) 14 | 58 | 0.4 |
| TEG dimethacrylate (NK エ ス テ Le 4G, Xin Zhong village chemistry) | 14 | 0.5 |
| 1,6-hexanediol dimethacrylate (NK エ ス テ Le HD-N, Xin Zhong village chemistry) | 6 | 0.5 |
| Neopentylglycol dimethacrylate (NK エ ス テ Le NPG, Xin Zhong village chemistry) | 7 | 0.0 |
| 2-hydroxyl-1,3-dimethyl allene acyloxy propane (NK エ ス テ Le 701, Xin Zhong village chemistry) | 37 | 0.6 |
| 1,4-butylene glycol dimethacrylate (BD, Xin Zhong village chemistry) | 7 | 2.0 |
| Polyfunctional monomer | ||
| The material name | Viscosity (mPas) | P.I.I. |
| Trimethylolpropane trimethacrylate (NK エ ス テ Le TMPT, Xin Zhong village chemistry) | 42 | 0.8 |
| TriMethylolPropane(TMP) modification triacrylate (VISCOAT#360, Osaka organic) | 55 | 1.5 |
| TriMethylolPropane(TMP) PO modification triacrylate (ニ ユ one Off ロ Application テ イ ア TMP-3P, the first industrial pharmacy) | 60 | 0.1 |
| Glycerine PO modification triacrylate (VISCOAT#GPT, Osaka organic) | 75 | 0.8 |
Wherein, the viscosity in the above-mentioned table is the measured value under 25 ℃.
Color inks of the present invention and achromaticity ink can use tensio-active agent, for example as the silicone-based tensio-active agent, preferably use polyester modification silicone or polyether modified silicone, preferred especially polyether-modified polydimethylsiloxane or the silicone of using.As object lesson, can enumerate K-347, BYK-348, BYK-UV3500,3510,3530,3570 (Chemie Japan Co., Ltd. system).
In color inks of the present invention and achromaticity ink, can contain polymerization starter.As polymerization starter, be not particularly limited, but preferably contain more than amine compound, thioxanthone, polymerizability particulate any, for example can enumerate Darocur EHA, EDB (CIBASPECIALTY CHEMICALS corporate system) as Aminobenzoate, thioxanthone, isopropyl thioxanthone, dimethyl thioxanthone, diethyl thioxanthone, to its surface to as the polymerizability particulate etc. of polymerizability functional group.
In addition, for the light that will shine is used for polyreaction effectively, can add sensitizing agent.As sensitizing agent, can enumerate the pigment derivative of coumarin series, cyanine system, anthracene system etc.
In addition, color inks of the present invention and achromaticity ink preferably contain the hot radical polymerization retarder.Thus, the storage stability of composition for ink is improved.Can use and in the hot radical polymerization retarder, be combined with the material that general Polymerizable composition obtains, be antioxidant for example except phenol, sterically hindered phenolic compound, hindered amine light stabilizer (HALS), phosphorous antioxidant, be widely used in outside the Hydroquinone monomethylether of (methyl) Acrylic Acid Monomer, can enumerate quinhydrones, tert-butyl catechol, pyrogallol etc., but preferred sterically hindered phenolic compound or HALS based compound, as sterically hindered phenolic compound, can enumerate Irgastab UV-22, as the HALS based compound, can enumerate Irgastab UV-10 (CIBA SPECIALTY CHEMICALS corporate system).
Color inks of the present invention comprises yellow ink, magenta ink, cyan, as their light yellow ink, shallow magenta ink, the pale cyan inks of light ink, as red ink, green ink, blue ink, orange ink, brown ink and the purple ink etc. of secondary color.
Achromaticity ink of the present invention comprises black ink, white ink, grey chromatic ink, light/dark balance ink and transparent ink etc.Transparent ink is meant the water white ink with look material.
In addition, the look material in color inks of the present invention and achromaticity ink is from the viewpoint of the weather resistance of print, preferred pigments.
Pigment as using in the present invention is not particularly limited, but can uses mineral dye, pigment dyestuff.
As mineral dye, except titanium oxide and ferric oxide, the carbon black that can use known method such as utilizing contact process, oven process, hot method to make.In addition, as pigment dyestuff, can use azo pigment (containing azo colour lake, insoluble azo colour, condensed azo-pigment, chelating azo pigment etc.), polycycle pigment (for example phthalocyanine pigment, perylene pigment, purple cyclic ketones pigment, anthraquinone pigment, quinoline a word used for translation ketone pigment, two piperazine pigment, thioindigo color, isoindoline ketone pigment, Kui phthalein ketone pigment etc.), dyestuff sequestrant (for example basic dye type sequestrant, acidic dye type sequestrant etc.), nitropigments, nitroso pigments, nigrosine etc.
With regard to the object lesson of pigment, as carbon black, can enumerate C.I. Pigment black 7, the No.2300 of Mitsubishi Chemical Ind's system, No.900, MCF88, No.33, No.40, No.45, No.52, MA7, MA8, MA100, No.2200B etc., the Raven 5750 of Columbia Co., Ltd's system, Raven5250, Raven 5000, Raven 3500, Raven 1255, Raven 700 etc., the Regal 400R of Cabot corporate system, Regal 330R, Regal 660R, Mogul L, Mogul 700, Monarch800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch1300, Monarch 1400 etc., the color black of Degussa corporate system (Color Black) FW1, color black FW2V, color black FW18, color black FW200, color black S150, color black S160, color black S170, Printex 35, Printex U, PrintexV, Printex 140U, Special Black 6, Special Black 5, Special Black 4A, SpecialBlack 4 etc.
As the pigment that in white ink, uses, can enumerate titanium dioxide, lime carbonate, calcium sulfate, zinc oxide, barium sulfate, barium carbonate, silicon-dioxide, aluminum oxide, kaolin, clay, talcum, carclazyte, aluminium hydroxide, magnesiumcarbonate etc., preferably the mixture of one or more that from the group that these pigment constitute, select.
And then, can use the proportion white hollow resin littler than mineral dyes such as titanium dioxide, preferably mix use with above-mentioned mineral dye.Such white hollow resin can use commercially available material, for example can suitably use " ロ one ペ イ Network OP-84J ", " ロ one ペ イ Network OP-62 ", " the ロ one ペ イ Network HP-91 " of ロ one system ア Application De Ha one ス company, " SX863A " of JSR Corp., " SX866B ", " ボ Application コ one ト " of イ Application キ chemical company, " グ ラ Application De one Le PP-1000 ", " グ ラ Application De one Le PP-1001 ", " グ ラ Application De one Le PP-2000 ", " the ラ テ Star Network ス SBL8801 " of Asahi Chemical Industry's industry etc.
As the pigment that is used for yellow ink, can enumerate C.I. Pigment Yellow 73 1,2,3,12,13,14,16,17,73,74,75,83,93,95,97,98,109,110,114,120,128,129,138,139,150,151,154,155,180,185,213 etc.
In addition, as the pigment that is used for magenta ink, can enumerate C.I. Pigment red 5,7,12,48 (Ca), 48 (Mn), 57 (Ca), 57:1,112,122,123,168,184,202,209, C.I. pigment violet 19 etc.
And then, as the pigment that is used for cyan ink, can enumerate C.I. pigment blue 1,2,3,15:3,15:4,15:34,16,22 etc.
Other color inks making, can also use normally used pigment except mixing above-mentioned ink.
In addition, as the pigment that can be used for metallic ink, be not particularly limited, for example can enumerate by on the flat substrates face, stack gradually peel off the structure that obtains with resin layer and metal level or alloy layer or stack gradually peel off the structure that obtains with resin layer and metal or alloy layer and silicon dioxide layer form compoundization pigment substance, be that peel off and chippy material from above-mentioned flat substrates on the border with above-mentioned metal or alloy layer and above-mentioned interface of peeling off with resin layer.
The metal that uses at the metal or alloy layer of the compoundization pigment substance that is used for making this tinsel, so long as have the metal that metalluster etc. has function, just be not particularly limited, can use aluminium, silver, gold, nickel, chromium, tin, zinc, indium, titanium, copper etc., can also use they elemental metals or their alloy or their mixture at least a.In addition, versicolor pigment can also mix mutually and use in order to regulate its tone.For example, become and have cyan in order to have red black tone, also can hybrid pigment black 7 and pigment Blue 15: 3.In addition, can also add white dyes.
By preferred implementation of the present invention, preferred its median size of inorganic pigment dyestuff is the pigment of the scope of 10n～200nm, more preferably the pigment about 50nm～150nm.As metallic pigment, preferred median size is that the above 100nm of 15nm is following, 50% volume average particle size is that the above 4.0 μ m of 1.0 μ m are following, more preferably the maximum particle diameter in following, the size-grade distribution of the above 1.0 μ m of 1.0 μ m is that maximum particle diameter during 12 μ m are following, preferred size distributes is the tinsels below the 5 μ m.
Scope about the preferred 0.1 weight % of the addition of the look material of composition for ink～25 weight %, the more preferably scope about 0.5 weight %～15 weight %.
By preferred implementation of the present invention, these pigment can be used as the dispersible pigment dispersion that obtains with dispersion agent or surfactant-dispersed in aqueous medium become color inks or achromaticity ink.As preferred dispersing agent, can use habitual dispersion agent, for example macromolecule dispersing agent of preparation dispersible pigment dispersion.
In addition, with regard to light-cured type ink group of the present invention, when ink contained coloured material, it is a plurality of that the ink that contains this look material can be that each color has.For example, except basic 4 looks of yellow, carmetta, cyan, black, when heavy colour that in each color, adds same train respectively or light color, except carmetta, can enumerate the shallow carmetta of light color, the redness of heavy colour, except cyan, can also enumerate the light cyan of light color, the blueness of heavy colour, purple.Perhaps, the green of all right secondary color, orange.And then except achromatic black, can also enumerate grey as its light color, light/dark balance, as the unglazed black of heavy colour, equally except achromatic white, can also enumerate cream color, ivory white, and then in addition, so long as metallic color can be enumerated silver color, gold, coppery, chromium silver color etc.
In addition, can also add levelling additive, matting agent, the polyester based resin that is used to regulate the film rerum natura, polyurethane series resin, vinyl resin, acrylic resin, rubber as required is resin, polyacrylic acid polyol resin, polyoxy alkylidene polyalkylene polyimide resin, wax class.Other public compositions that in addition, can in ink of the present invention, add wetting agent, soak into solvent, conduct such as pH regulator agent, sanitas, mould inhibitor can be used for two-component-type photocuring ink.
Color inks of the present invention can be by mixing with the achromaticity ink and with its curing, particularly mixing with transparent ink mostly.Achromaticity ink of the present invention can be used the achromaticity ink cured separately, as the solidified method, has to make its solidified situation, mix the situation of achromaticity ink, three kinds of situations of situation of mixed colors ink with the achromaticity ink separately.Requiring the black ink of identification, requiring in the concealed white ink, preferably make its curing separately.
Light-cured type ink group of the present invention when mixing the ink of 2 kinds, is cured reaction by irradiates light after mixing.Mix so long as before curing reaction, just can be before printing or after printing.That is, this mixing and printing can be to adhere to 2 kinds of inks and make its blended form on the same position on the recording medium on recording medium, can also be to mix 2 kinds of inks and make it attached to the form on the recording medium in addition.
As the ink jet recording method of the printing process of having used photocuring composition for ink group of the present invention, be on recording medium, to spray the composition for ink method of irradiation ultraviolet radiation then.
Radiation source is not particularly limited the light of the wavelength that the above 450nm of the preferred 350nm of radiation source is following.The ultraviolet irradiation amount is 10mJ/cm
2Above 20000mJ/cm
2Below, in addition preferably at 50mJ/cm
2Above 15000mJ/cm
2Carry out in the following scope.As long as the ultraviolet irradiation amount in this kind extent and scope just can fully be cured reaction.
Uviolizing can be enumerated lamps such as metal halide lamp, xenon lamp, carbon arc lamp, chemistry lamp, low pressure mercury lamp, high voltage mercury lamp.For example can use commercially available the waiting such as H lamp, D lamp, V lamp of Fusion System corporate system to carry out.
In addition, utilize luminescence-utraviolet semiconductor elements such as ultraviolet LED (ultraviolet LED) or luminescence-utraviolet semiconductor laser, can carry out uviolizing.
In addition, utilize, can on recording medium, carry out the record that needs as the record ink-jet recording device that has used the printing device of light-cured type ink group of the present invention.
In addition, can use light-cured type ink group of the present invention to form the print of a part that has formed image at least.Material to print is not particularly limited.
Embodiment 1
Below, utilize embodiment that the present invention is described in more detail, but the present invention is not limited to these embodiment.In addition, in following table, fit in component and represent with weight %.
The preparation of black ink composition 1 (Bk1)
Preparation is by forming black ink composition 1 forming of following table 2.Preparation is carried out according to following main points.Mix to stir C.I. Pigment black 715 weight parts, as polyoxy alkylidene addition polyalkylene amine (the first industrial system デ イ ス コ one Le N-518 of drugmaker) 5 weight parts, ethylene glycol monoallyl ether (being designated hereinafter simply as AG) 80 weight parts of dispersion agent, as mixture, use sand mill (the peace river makes made), (diameter 1.5mm) disperseed 6 hours with the zirconium dioxide pearl.Separate the zirconium dioxide pearl with separator then and obtain dispersible pigment dispersion A.
Then, mix solvent beyond AG, pigment and the dispersion agent in the gradation composition shown in the following table 2 and various additive and it is dissolved fully, make ink solvent, the limit is stirred above-mentioned dispersible pigment dispersion A limit and is slowly dripped in ink solvent then, finishes the back and mixes under normal temperature and stirred 30 minutes dripping.Then, filter with the membrane filter of 5 μ m, as black ink composition as follows 1.
Table 2
| Black ink 1 (Bk1) | Transparent ink 1 (CL1) | Black ink 2 (Bk2) | Black ink 3 (Bk3) | Black ink 4 (Bk4) | |
| C.I. Pigment black 7 | 6.0 | - | 3.0 | 9.0 | 6.0 |
| N-518 | 2.0 | - | 1.0 | 3.0 | 2.0 |
| NVF | 25.0 | 25.0 | 25.0 | 25.0 | 25.0 |
| AG | 47.6 | 53.6 | 49.6 | 43.6 | 55.6 |
| STAR-501 | 10.0 | 15.0 | 12.0 | 10.0 | 10.0 |
| BYK-3570 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Irgacure 819 | 6.4 | 4.0 | 6.4 | 6.4 | - |
| Irgacure 369 | 1.6 | - | 1.6 | 1.6 | - |
| Irgacure 127 | - | 1.0 | - | - | - |
| Darocur EDB | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
| kgastab UV- 10 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
The preparation of water white transparency ink (transparent ink) composition 1 (CL1)
The described gradation composition of above-mentioned table 2 is mixed and it is dissolved fully, stirred at normal temperatures 30 minutes.Membrane filter with 5 μ m filters then, prepares water white transparency ink (transparent ink) composition 1 shown in the above-mentioned table 2.
Black ink composition 2～4 (preparation of Bk2～Bk4)
Utilize and black ink composition 1 (Bk1) identical operations, (Bk2～Bk4) also is the composition of above-mentioned table 2 to preparation black ink composition 2～4.
The preparation of white ink composition 1 (W1)
The method for making of titanium dioxide fine particles
Obtain titanium sulfate solution with the sulfuric acid dissolution titaniferous ore.In the oxidizing aqueous titanium that this titanium sulfate solution of hydrolysis obtains, with respect to using TiO
2100 weight parts that convert add the ammonium phosphate of 0.50 weight part, the vitriolate of tartar of 0.30 weight part, the Tai-Ace S 150 of 0.30 weight part, reach 1020 ℃ with the oxidizing aqueous titanium of rotation retort furnace internal heating until the product temperature in the laboratory.The titanium dioxide fine particles that generates is cooled to room temperature, observes with the infiltration type electron micrograph, the result is judged as the anatase titanium dioxide of average primary particle diameter 0.13 μ m.Mixing as its implemented carbonic acid gas particulate 15 weight parts of surface-treated white pigment, as the polyoxy alkylidene addition polyalkylene amine of dispersion agent (the first industrial system デ イ ラ コ one Le N-518 of drugmaker) 5 weight parts, ethylene glycol but allyl ethers (being designated hereinafter simply as AG) 80 weight parts, with sand mill (the peace river makes made) filling zirconium dioxide pearl (1.0mm diameter) and loading level is 1.5 times of amounts of slip, after disperseing 2 hours, remove pearl, obtain the 60wt% monomer dispersion liquid of titanium dioxide fine particles (C.I. Pigment white 6).Then by with black ink composition 1 identical operations, preparation white ink composition 1 also makes it have the composition of following table 3.
Table 3
| White ink 1 (W1) | White ink 2 (W2) | White ink 3 (W3) | White ink 4 (W4) | |
| C.I. Pigment white 6 | 6.0 | 3.0 | 9.0 | 6.0 |
| N-518 | 2.0 | 1.0 | 3.0 | 2.0 |
| NVF | 25.0 | 25.0 | 25.0 | 25.0 |
| AG | 47.6 | 49.6 | 43.6 | 55.6 |
| STAR-501 | 10.0 | 12.0 | 10.0 | 10.0 |
| BYK-3570 | 0.2 | 0.2 | 0.2 | 0.2 |
| Irgacure 819 | 6.4 | 6.4 | 6.4 | - |
| Irgacure 369 | - | 1.6 | 1.6 | - |
| Irgacure 127 | 1.6 | - | - | - |
| Darocur EDB | 1.0 | 1.0 | 1.0 | 1.0 |
| Irgastab UV- 10 | 0.2 | 0.2 | 0.2 | 0.2 |
White ink composition 2～4 (preparation of W2～W4)
Utilize and white ink composition 1 (W1) identical operations preparation white ink composition 2～4 (W2～W4) make it become the composition of above-mentioned table 3.
The preparation of black ink composition 5 (Bk5), white ink composition 5 (W5)
Utilize and black ink composition 1 (Bk1) identical operations, prepare black ink composition 5, white ink composition 5 that following table 4 cooperates.
The preparation of black ink composition 6 (Bk6)
Except not using the optical free radical polymerization starter, utilize and the identical method of black ink composition 1 (Bk1), make the black ink composition 6 of the cooperation of following table 5.
The preparation of white ink composition 6 (W6)
Except not using the optical free radical polymerization starter, utilize and the identical method of white ink composition 1 (W1), make the white ink composition 6 of the cooperation of following table 5.
Table 4
| Black ink 5 (Bk5) | White ink 5 (W5) | |
| Pigment | C.I. deceive 7 | C.I. white 6 |
| 6.0 | 9.0 | |
| N-518 | 2.0 | 3.0 |
| NVF | 25.0 | - |
| AG | 47.6 | 58.6 |
| V#1000 | 14.0 | 25.0 |
| BYK-3570 | 0.2 | 0.2 |
| Irgacure 819 | 3.2 | 3.2 |
| Irgacure 369 | 0.8 | - |
| Irgacure 127 | - | 0.8 |
| Darocur EDB | 1.0 | - |
| Irgastab UV-10 | 0.2 | 0.2 |
Table 5
| Black ink 6 (Bk6) | White ink 6 (W6) | |
| Pigment | C.I. deceive 7 | C.I. white 6 |
| 6.0 | 9.0 | |
| N-518 | 2.0 | 3.0 |
| NVF | 25.0 | - |
| AG | 51.6 | 62.6 |
| V#1000 | 14.0 | 25.0 |
| BYK-3570 | 0.2 | 0.2 |
| Darocur EDB | 1.0 | - |
| Irgastab UV-10 | 0.2 | 0.2 |
Below, the compound described in the indicator gauge.
N-518: polyoxy alkylidene addition polyalkylene amine (the first industrial system デ イ ス コ one Le N-518 of drugmaker)
NVF:N-vinyl formamide (waste river chemical industrial company system)
AG: one or two those mono allyl ethers (Japanese emulsifying agent corporate system) of leaving hospital
STAR-501: hyperbranched polymer (Osaka organic chemistry industrial system)
BYK-UV3570: polyether modified silicone is tensio-active agent (a Chemie Japan corporate system)
Irgacure 819: optical free radical polymerization starter B (CIBA SPECIALTY CHEMICALS corporate system)
Irgacure 369: optical free radical polymerization starter B (CIBA SPECIALTY CHEMICALS corporate system)
Irgacure 127: optical free radical polymerization starter B (CIBA SPECIALTY CHEMICALS corporate system)
Darocur EDB: polymerization promotor B (CIBA SPECIALTY CHEMICALS corporate system)
Irgastab UV-10: hot radical polymerization starter B (CIBA SPECIALTYCHEMICALS corporate system)
V#1000:VISCOAT#1000 (Osaka organic chemistry industry system)
Lettering evaluation method 1
Use the ink group of above-mentioned various achromaticity inks, utilize the system ink-jet printer PM-G920 of Seiko Epson Corp, A ink kind is filled in the flat black row, B ink kind is filled in the gloss optimizer row, at normal temperatures and pressures, correspondence position at image is implemented image printing with A ink kind, under the lettering condition that covers the entire image zone B ink kind is implemented image printing.The OHP film of use A4 size in recording medium (XEROX of Fuji corporate system, XEROX FILM＜no frame 〉).In addition, utilization has 60mW/cm
2The uviolizing light source of irradiation dose, become in the integration light quantity under the condition of cure of the numerical value shown in the table and carry out lettering and solidification treatment.
The measuring method of OD value
The photo that working sample is arranged on Seiko Epson system is with paper＜gloss〉on (sample number KA450PSK).Use spectral photometric colour measuring meter Gretag-Macbeth corporate system SPM-50 to measure the OD value of black lettering portion.
L
*The measuring method of value
Working sample is arranged on the black plate of OD value=1.64, uses spectral photometric colour measuring meter Gretag-Macbeth corporate system SPM-50 to measure the L of white lettering portion
*Value.
Lettering evaluation, L with black ink, transparent ink and white ink
*Values etc. are shown in table 6 and table 7.
Table 6
| A ink kind | B ink kind | The body of printed matter (wt%) | The thickness of printed matter (μ m) | Solidify necessary integrated exposure (mJ/cm 2) | Optical concentration (OD value) | Solidified nature | |
| Embodiment 1 | Black 1 | - | 6.0 | 18 | 10800 | 2.4 | A |
| Embodiment 2 | Black 3 | Black 2 | 6.0 | 35 | 10800 | 2.5 | A |
| Embodiment 3 | Black 3 | Transparent 3 | 4.5 | 30 | 7500 | 2.2 | A |
| Embodiment 4 | Black 1 | Black 3 | 7.5 | 18 | 14000 | 2.5 | A |
| Embodiment 5 | Black 5 | - | 6.0 | 18 | 12600 | 2.5 | A |
| Comparative example 1 | Black 4 | - | 6.0 | 18 | ＞14000 | - | C |
| Comparative example 2 | Black 6 | - | 6.0 | 18 | ＞14000 | - | C |
Table 7
| A ink kind | B ink kind | The body of printed matter (Wt%) | The thickness of printed matter (μ m) | Solidify necessary integrated exposure (mJ/cm 2) | L *Value | Solidified nature | |
| Embodiment 6 | White 1 | - | 6.0 | 16 | 10800 | 59.2 | A |
| Embodiment 7 | White 3 | White 2 | 6.0 | 34 | 10800 | 63.0 | A |
| Embodiment 8 | White 3 | Transparent 3 | 4.5 | 32 | 7500 | 58.7 | A |
| Embodiment 9 | White 1 | White 3 | 7.5 | 19 | 14000 | 63.4 | A |
| Embodiment 10 | White 5 | - | 6.0 | 17 | 11400 | 60.2 | A |
| Comparative example 3 | White 4 | - | 6.0 | 17 | ＞14000 | - | C |
| Comparative example 4 | White 6 | - | 6.0 | 17 | ＞14000 | - | C |
The index of solidified nature
A: fully solidify and no problem level in practicality
B: partly solidified, solidified nature is insufficient
C: do not solidify fully
The preparation of yellow ink composition 1 (Y1)
Preparation is by the following yellow ink composition that forms of forming.Preparation is carried out according to following main points.Mix to stir C.I. Pigment Yellow 73 151 15 weight parts, as polyoxy alkylidene addition polyalkylene amine (the first industrial system デ イ ス コ one Le N-518 of drugmaker) 5 weight parts, ethylene glycol monoallyl ether (being designated hereinafter simply as AG) 80 weight parts of dispersion agent, as mixture, use sand mill (the peace river makes made), (diameter 1.5mm) disperseed 6 hours with the zirconium dioxide pearl.Separate the zirconium dioxide pearl with separator then and obtain dispersible pigment dispersion B.
Then, the same with black ink composition 1, mix solvent beyond the pigment of following gradation composition kind and the dispersion agent and various additive and it is dissolved fully, make after the ink solvent, the limit is stirred above-mentioned dispersible pigment dispersion B limit and is slowly dripped in the ink solvent, mixes under the end back normal temperature that drips and stirs 30 minutes.Then, filter, make the yellow ink composition shown in the following table 8 with the membrane filter of 5 μ m.
Table 8
| Yellow ink 1 (Y1) | Magenta ink 1 (M1) | Cyan 1 (C1) | |
| Pigment | C.I. yellow 151 | C.I. purple 19 | C.I. blue 15:3 |
| 6.0 | 6.0 | 6.0 | |
| N-518 | 2.0 | 2.0 | 2.0 |
| NVF | 25.0 | 25.0 | 25.0 |
| AG | 55.6 | 55.6 | 55.6 |
| STAR-501 | 10.0 | 10.0 | 10.0 |
| BYK-3570 | 0.2 | 0.2 | 0.2 |
| Darocur EDB | 1.0 | 1.0 | 1.0 |
| Irgastab UV-10 | 0.2 | 0.2 | 0.2 |
The preparation of magenta ink composition 1 (M1), cyan composition 1 (C1)
Utilize and the identical method of yellow ink composition 1 (Y1), prepare magenta ink composition 1, the cyan composition 1 of above-mentioned table 8.
The preparation of yellow ink composition 2 (Y2), magenta ink composition 2 (M2), cyan composition 2 (C2)
Utilize and the identical method of yellow ink composition 1 (Y1), prepare yellow ink composition 2, magenta ink composition 2, the cyan composition 2 of the cooperation of following table 9.
The preparation of transparent ink composition 2 (CL2)
Utilize and the identical method of transparent ink composition 1 (CL1), prepare the transparent ink composition 2 of the cooperation of following table 10.
The preparation of yellow ink composition 3 (Y3), magenta ink composition 3 (M3), cyan composition 3 (C3)
With regard to the yellow ink composition 3 of the cooperation of following table 11, magenta ink composition 3, cyan composition 3, make the dispersible pigment dispersion B that contains optical free radical polymerization starter, dispersion agent and pigment in advance with the described cooperation of table 11, solvent beyond optical free radical polymerization starter, dispersion agent and the pigment shown in the mixture table 11 and various additive also dissolve it fully, make ink solvent, add, mix above-mentioned dispersible pigment dispersion B then, in addition, make with the method identical with yellow ink composition 1 (Y1).
The preparation of transparent ink composition 3 (CL3)
Except not using the Photoepolymerizationinitiater initiater, utilize and the identical method of transparent ink composition 1 (CL1), prepare the transparent ink composition 3 of the cooperation of following table 12.
The preparation of shallow magenta ink composition 1 (LM1), pale cyan inks composition 1 (LC1), red ink composition 1 (R1), green ink composition 1 (GR1), orange composition for ink 1 (OR1)
Utilize and the identical method of yellow ink composition 1 (Y1), prepare shallow magenta ink composition 1, pale cyan inks composition 1, red ink composition 1, green ink composition 1, the orange composition for ink 1 of the cooperation of following table 13.
The preparation of grey composition for ink 1,2 (G1,2)
Utilize and the identical method of black ink composition 1 (Bk1), prepare the grey composition for ink 1,2 of the cooperation of following table 14.
Table 9
| Yellow ink 2 (Y2) | Magenta ink 2 (M2) | Cyan 2 (C2) | |
| Pigment | C.I. yellow 213 | C.I. purple 19 | C.I. blue 15:3 |
| 5.0 | 6.0 | 4.0 | |
| N-518 | 2.0 | 2.0 | 1.5 |
| AG | 67.6 | 66.6 | 69.1 |
| V#1000 | 25.0 | 25.0 | 25.0 |
| BYK-3570 | 0.2 | 0.2 | 0.2 |
| Irgastab UV-10 | 0.2 | 0.2 | 0.2 |
Table 10
| Transparent ink 2 (CL2) | |
| Pigment | - |
| - | |
| N-518 | - |
| NVF | - |
| AG | 70.6 |
| V#1000 | 25.0 |
| BYK-3570 | 0.2 |
| Irgacure 819 | 3.2 |
| Irgacure 369 | - |
| Irgacure 127 | 0.8 |
| Darocur EDB | - |
| Irgastab UV-10 | 0.2 |
Table 11
| Yellow ink 3 (Y3) | Magenta ink 3 (M3) | Cyan 3 (C3) | |
| Pigment | C.I. yellow 213 | C.I. purple 19 | C.I. blue 15:3 |
| 5.0 | 6.0 | 4.0 | |
| N-518 | 2.0 | 2.0 | 1.5 |
| AG | 63.6 | 62.6 | 65.1 |
| V#1000 | 25.0 | 25.0 | 25.0 |
| BYK-3570 | 0.2 | 0.2 | 0.2 |
| Irgacure 819 | 3.2 | 3.2 | 3.2 |
| Irgacure 369 | 0.8 | 0.8 | 0.8 |
| Irgacure 127 | - | - | - |
| Irgastab UV-10 | 0.2 | 0.2 | 0.2 |
Table 12
| Transparent ink 3 (CL3) | |
| Pigment | - |
| - | |
| N-518 | - |
| NVF | - |
| AG | 74.6 |
| V#1000 | 25.0 |
| BYK-3570 | 0.2 |
| Darocur EDB | - |
| Irgastab UV-10 | 0.2 |
Table 13
| Shallow carmetta 1 (LM1) | Light cyan 1 (LC1) | Red 1 (R1) | Green 1 (GR1) | Orange 1 (OR1) | |
| Pigment | C.I. red 122 | C.I. blue 15:3 | C.I. red 177 | C.I. green 7 | C.I. the orange 43 |
| 1.0 | 1.0 | 3.0 | 3.0 | 3.0 | |
| N-518 | 0.3 | 0.3 | 1.0 | 1.0 | 1.0 |
| AG | 70.3 | 70.3 | 70.6 | 70.6 | 70.6 |
| V#1000 | 28.0 | 28.0 | 25.0 | 25.0 | 25.0 |
| BYK-3570 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Irgastab UV-10 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Ash chromatic ink 1 (G1) | Ash chromatic ink 2 (G2) | |
| Pigment | C.I. deceive 7 | C.I. deceive 7 |
| 2.0 | 1.0 | |
| N-518 | 1.0 | 0.5 |
| NVF | - | - |
| AG | 64.6 | 66.1 |
| V#1000 | 28.0 | 28.0 |
| BYK-3570 | 0.2 | 0.2 |
| Irgacure 819 | 3.2 | 3.2 |
| Irgacure 369 | - | - |
| Irgacure 127 | 0.8 | 0.8 |
| Darocur EDB | - | - |
| Irgastab UV-10 | 0.2 | 0.2 |
Lettering evaluation method 2
Use various ink groups, utilize the system ink-jet printer PM-G920 of Seiko Epson Corp, according to the ink configuration of table 5, at normal temperatures and pressures, under the lettering condition that water white transparency ink bullet falls such, respectively to implementing the full-colour image printing on the correspondence position of black, white, color inks.The OHP film of use A4 size in recording medium (XEROX of Fuji corporate system, XEROXFILM＜no frame 〉).In addition, utilization has total 120mW/cm
2The uviolizing light source of irradiation dose, become 14400mW/cm in the integration light quantity
2Carry out lettering and solidification treatment under such condition of cure, confirm to have been implemented the full-colour image of solidification treatment.
The configuration of table 15 P M-G920 composition for ink
| The Y row | The M row | The C row | The Bk row | The MK row | The R row | The B row | The GO row | Solidified nature | |
| Embodiment 11 embodiment 12 embodiment 13 embodiment 14 embodiment 15 embodiment 16 embodiment 17 embodiment 18 | Y1 Y2 Y2 Y2 Y2 Y2 Y2 Y2 | M1 M2 M2 M2 M2 M2 M2 LM1 | C1 C2 C2 C2 C2 C2 C2 LC1 | Bk1 Bk5 Bk5 Bk5 Bk5 Bk6 Bk5 Bk5 | Bk1 Bk5 G1 G2 G1 Bk6 G1 G1 | W1 W5 R1 R1 R1 W6 LM1 R1 | W1 W5 GR1 GR1 OR1 W6 LC1 GR1 | CL1 CL2 CL2 CL2 CL2 CL2 CL2 CL2 | A A A A A A A A |
| Comparative example 5 comparative examples 6 comparative examples 7 | Y3 Y2 Y3 | M3 M2 M3 | C3 C2 C3 | Bk6 Bk6 Bk1 | Bk6 Bk6 Bk1 | W6 W6 W1 | W6 W6 W1 | CL3 CL3 CL1 | B C B |
The index of solidified nature
A: shades of colour all fully solidifies and no problem level in practicality
B: partly solidified, solidified nature is insufficient
C: shades of colour does not all solidify fully
As can be known from the above results, the achromaticity ink of the photocuring ink group of various embodiments of the present invention, the body of its printed matter is enough, has outstanding L
*Value, and solidified nature can obtain gratifying result, can be enough to use.In addition, use the achromaticity ink and the color inks of the photocuring ink group of various embodiments of the present invention, can obtain having enough solidified nature and high-resolution image, can be enough to as can be known as light-cured type ink group.
Claims (10)
1. a light-cured type ink group is characterized in that, contains:
Do not contain the optical free radical polymerization starter color inks and
At least the achromaticity ink that contains the optical free radical polymerization starter more than a kind.
2. light-cured type ink group as claimed in claim 1 is characterized in that,
The achromaticity ink comprises black ink, white ink, grey chromatic ink, light/dark balance ink and transparent ink.
3. as claim 1 or 2 described light-cured type ink groups, it is characterized in that,
White ink contains hollow resin.
4. as any described light-cured type ink group in the claim 1～3, it is characterized in that,
Color inks is to be selected from yellow ink, magenta ink, cyan, as their light yellow ink, shallow magenta ink, the pale cyan inks of light ink, as in red ink, green ink, blue ink, orange ink, brown ink and the purple ink of secondary color more than one.
5. printing process of having used any described light-cured type ink group in the claim 1～4.
6. printing process as claimed in claim 5 is characterized in that,
The achromaticity ink is solidified separately.
7. printing process as claimed in claim 5 is characterized in that,
The achromaticity ink is mixed with other achromaticity inks and solidify.
8. as any described printing process in the claim 5～7, it is characterized in that,
Color inks is solidified by mixing with the achromaticity ink.
9. printing device that has used any described light-cured type ink group in the claim 1～4.
10. one kind is used any print that described light-cured type ink group prints in the claim 1～4.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006225736 | 2006-08-22 | ||
| JP2006225736 | 2006-08-22 | ||
| JP2007178979 | 2007-07-06 |
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| Publication Number | Publication Date |
|---|---|
| CN101130648A true CN101130648A (en) | 2008-02-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200710141751 Pending CN101130648A (en) | 2006-08-22 | 2007-08-21 | Photocurable ink set, and printing method, printing apparatus and printed matter each using the same |
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| CN102585598A (en) * | 2008-03-24 | 2012-07-18 | Dnp精细化工股份有限公司 | Oil ink set |
| CN103048877A (en) * | 2011-10-14 | 2013-04-17 | 武汉海蓝生物技术有限公司 | Ink-jet printing silk screen plate making method and photo-sensitive resist ink thereof |
| CN103547640A (en) * | 2011-05-18 | 2014-01-29 | 株式会社理光 | Photopolymerizable inkjet ink, ink cartridge, and printer |
| CN104924765A (en) * | 2014-03-19 | 2015-09-23 | 精工爱普生株式会社 | Maintenance liquid and maintenance method |
| CN107011737A (en) * | 2016-01-28 | 2017-08-04 | 精工爱普生株式会社 | Ink composite group |
| CN108624123A (en) * | 2017-03-17 | 2018-10-09 | 精工爱普生株式会社 | Oiliness ink jet recording liquid |
| CN111263701A (en) * | 2017-09-15 | 2020-06-09 | 大日本印刷株式会社 | Information recording medium, and booklet |
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2007
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