CN100424141C - Ultraviolet-ray solidified ink and printed matter using same - Google Patents
Ultraviolet-ray solidified ink and printed matter using same Download PDFInfo
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- CN100424141C CN100424141C CNB021188920A CN02118892A CN100424141C CN 100424141 C CN100424141 C CN 100424141C CN B021188920 A CNB021188920 A CN B021188920A CN 02118892 A CN02118892 A CN 02118892A CN 100424141 C CN100424141 C CN 100424141C
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Abstract
The present invention provides printing ink which simultaneously has favorable printing adaptability and tractability of oil printing ink and can be instantly dried by ultraviolet solidification. The present invention also provides a printed product using the printing ink. Moreover, the present invention provides printing ink used in an ultraviolet solidification printing method for continuously overprinting transparent varnish with ultraviolet solidification, which is the printing ink with good printing operation, high quality and ultraviolet solidification, wherein the printing ink overcomes the problems of total elimination and heavy metal residue by using oil printing ink. The present invention also provides the printed product which is better, more lustrous and more favorable in friction resistance by using the printing ink. Main varnish with ultraviolet solidification is regulated, and the main varnish forms requisite carrier components for the printing ink with ultraviolet solidification, so favorable lipophilicity is formed. Moreover, sufficient ultraviolet solidification is offered to the printing ink, and consequently, the present invention simultaneously has favorable printing adaptability and tractability of oil printing ink, and the instant solidification characteristic of printing ink with ultraviolet solidification.
Description
Technical field
The ultra-violet solidified printing ink that uses when the present invention relates to use offset press on substrate materials such as paper or plastic film, to print.
And, relate to when using this ink printing, pay the print of high gloss and high abrasion wiping property by the chromatography transparent varnish.
Background technology
In the printing of using oxypolymerization drying type oil-based ink, because print need carry out drying with the time, so there is the low problem of operating efficiency.As the method for head it off, though used ultra-violet solidified printing ink, oil-based ink does not have and is suitable for lithographic performance, in addition, at the printing press of using with oil-based ink, when using ultra-violet solidified printing ink, also there are problems such as rubber rollers swelling.
In addition, as the method that reduces these problems, known have before this ink setting, the ultra-violet solidified transparent varnish of chromatography on oxypolymerization drying type oil-based ink continuously, utilize uviolizing exsiccant method, as have good printing adaptability of oil-based ink and processing ease concurrently and utilize ultraviolet curing at short notice the exsiccant printing process use.
Yet the print with above-mentioned printing process obtains owing to need the oil-based ink ability completely solidified of substrate for a long time, can reduce promptly so-called total shortcoming of eliminating (grossback) so gloss is passed in existence in time.In addition, use the situation of ultra-violet solidified printing ink to compare with substrate printing ink, the heavy metal siccative of required usefulness or the existence of oil series solvent composition can remain in the print environment is produced pollution problems in oxypolymerization type oil-based ink.And, after the printing, since dry insufficient, also there is the inferior problem of rub resistance.
In order to solve these problems, open in the flat 10-052948 number application openly the spy, a kind of printing ink with oil-based ink and two kinds of composition mixed types of ultra-violet solidified printing ink is disclosed, and the printing process of using this printing ink.
This is the printing ink that has mixed ultra-violet solidified composition in the former oil-based ink, by ultraviolet curing, after printing,, improved the anti-sticking page or leaf property of printing ink, realized the invention of the reduction of the reduction of print step step installation exercise and the operation of dusting only with the ink pellet surface drying.Yet, though obtained lithography adaptability with this printing ink near oil-based ink, owing to contain metal drier or oil series solvent composition, the problem that still has environmental pollution, and for the completely solidified drying, the same with oil-based ink, still there is the problem that needs for a long time.
In addition, the spy open clear 57-123272 number application open in, a kind of acrylate with Hydrogenated Bisphenol A is disclosed as main component, merge the invention of the ultra-violet solidified printing ink of light oil lysotype that uses petroleum resin or xylene resin.
This invention is compared with above-mentioned printing ink, though do not contain metal drier or volatile solvent composition, can finish ultraviolet curings drying in instantaneous in addition, still has following shortcoming, that is,
1) since in the printing ink viscosity of the main Acrylic Acid Monomer that uses very high, thereby the kind of the solid resin that is used in combination and addition be restricted, and is difficult to obtain sufficient printing adaptability;
2) functionality of main Acrylic Acid Monomer is very low, is difficult to obtain ultra-violet solidified fully;
3) in main Acrylic Acid Monomer during dissolved solids resin manufacture varnish, if use the high resin of softening temperature, then dissolving needs for a long time, and in addition, if use the low resin of softening temperature, then the ultra-violet solidified printing ink of gained is ultra-violet solidified inferior.
Summary of the invention
The object of the present invention is to provide and a kind ofly have the good printing adaptability of oil-based ink and the easy property handled concurrently and utilize the printing-ink of ultraviolet curing wink-dry and use the print of this printing ink.
In addition, provide a kind of presswork good high-quality ultra-violet solidified printing ink, the continuous ultra-violet solidified transparent varnish of chromatography on printing-ink, used printing ink in the printing process as ultraviolet curing has been eliminated the total elimination when using oil-based ink or the problem of heavy-metal residual.
In addition, by using this printing ink, provide that a kind of productivity is better, gloss and the better print of wear-resisting wiping.
Promptly, the invention provides a kind of ultra-violet solidified printing ink, it is characterized in that, contain varnish, this varnish has: the ultra-violet solidified monomer that mixes with normal hexane and in this monomer the dissolved resin, the described ultra-violet solidified monomer that mixes with normal hexane is multifunctional (methyl) acrylate with polyoxyalkylene block.
The present invention is by adjusting the ultra-violet solidified main varnish that constitutes necessary carrier components in the ultra-violet solidified printing ink, make it form good lipophilicity, and pay ultra-violet solidified fully, good print adaptability that can obtain oil-based ink simultaneously and the instantaneous solidification characteristic of handling easiness and ultra-violet solidified printing ink.
Particularly in order to pay the printing ink lipophilicity, preferably use the tolerance value of normal hexane is adjusted to varnish more than 4.
In addition, in the printing ink of the invention described above, the total amount that is preferably in ultra-violet solidified monomer immiscible in the normal hexane and prepolymer is below 30%.
In the printing ink of the invention described above, described resin is the mixture of one in vibrin and the petroleum resin and/or two kind, the vibrin that this vibrin is to use monobasic acid, polyhydric acid and multivalence alcohol to obtain, in the raw material when synthetic this vibrin, the shared ratio of aliphatics monobasic acid and/or alicyclic monobasic acid is in the scope of 15-80 quality %.
Use such lipophilicity varnish, and in order to obtain to have ultra-violet solidified material fully, by with multi-functional ultra-violet solidified monomer that normal hexane mixes in mix, dissolve the resin that mixes with it, can obtain uniform thick liquid.
Pass through aforesaid method, with the ultra-violet solidified printing ink of above-mentioned varnish as main carrier, because the lipophilicity height of carrier, so have the following advantages, promptly, present good emulsifying adaptability in the offset lithography that uses dumping processing solution, simultaneously, the impregnability in the elastomeric materials such as blanket that uses in offset press or roller is little.
In addition, can use general oil-based ink such as light oil to clean, but also former state use oil-based ink to print with printing press material, printing plate material with washing composition.
And ultra-violet solidified printing ink of the present invention has and the general the same easy printing of oil-based ink, simultaneously because with the main composition composition of multi-functional monomer as carrier, so ultra-violet solidified good.Therefore, substitute and use common oxypolymerization drying type oil-based ink, use this ultra-violet solidified printing ink to print, behind continuous thereon ultra-violet solidified transparent varnish of chromatography or the aqueous transparent varnish, solidifying the exsiccant print by the UV-lamp irradiation compares with the situation of using oil-based ink, gloss is good, it is little always to eliminate, and the wear-resisting wiping after the printing is also good.
Embodiment
Below describe the present invention in detail.
The ultra-violet solidified monomer that uses among the present invention is multifunctional (methyl) acrylate that has the polyoxyalkylene block and have free polymerizability unsaturated double-bond more than 2 in a molecule, mixes with normal hexane.
This multifunctional (methyl) is as long as acrylate has enough big molecular weight, the elastomeric material that can suppress to use in printing press soaks into and gets final product, can use any, as so ultra-violet solidified monomer, for example make and have polyether glycol and (methyl) vinylformic acid that the addition trialkylphosphine oxide obtains in the compound bearing active hydrogen at multivalence alcohols, amine etc. and carry out esterification, the polyoxyalkylene polyols polyacrylic ester that obtains.
Multivalence alcohol as use this moment for example has glycerine, trimethylolethane, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol or Sorbitol Powder.
As amine, thanomin, diethanolamine are for example arranged.
As the abovementioned alkyl oxide compound, oxyethane, propylene oxide, butylene oxide ring, trimethylene oxide (terramycin), tetrahydrofuran (THF) (tetrahydrofuran (THF)) are arranged.These trialkylphosphine oxides can use separately, also can mix use, and in order to form good intermiscibility with normal hexane, the carbonatoms of trialkylphosphine oxide is preferably more than 3 with respect to the ratio of oxygen atomicity.
Preferred several molecular-weight average of polyoxyalkylene polyols polyacrylic ester are 400-1500, more preferably 500-800.When molecular weight is too small, because the impregnability of printing press rubber rollers is become big, thereby the printing ink on printing press can not obtain satisfactory stability.In addition, when molecular weight was excessive, the acryl equivalent increased, the printing ink that can not obtain suiting ultra-violet solidified.
The functionality of polyoxyalkylene polyols polyacrylic ester is preferably 3-6.
Functionality is high more, and the acryl that imports in per 1 molecule is many more, and the ability that is cross-linked to form of printing ink increases, and ultra-violet solidified quickening still, if the acryl ratio in the monomer molecule is too high, then can damage the solvability in normal hexane.
Therefore, as the ultra-violet solidified monomer that uses among the present invention, most preferably for example average addition 4-9 mole propylene oxide and the polyoxytrimethylene Viscoat 295 that obtains in per 1 mole of trimethylol propane.
As the resin that uses among the present invention,, there is not particular restriction so long as the dissolved resin for printing ink gets final product in above-mentioned ultra-violet solidified monomer.As such resin, preferably use for example lipophilicity vibrin, petroleum resin, rosin ester resin etc.
As above-mentioned lipophilicity vibrin, during vibrin that use is obtained by monobasic acid, polyhydric acid and multivalence alcohol, can use in the raw material when synthesizing this resin, the shared ratio of aliphatics monobasic acid and/or alicyclic monobasic acid is the scope of 15-80 quality %, more preferably the vibrin of 20-65 quality % scope.
Promptly, when aliphatics monobasic acid and/or alicyclic monacid usage rate are lower than 15 quality %, the lipophilicity of gained vibrin is low, and the normal hexane tolerance value step-down during varnish uses the detergency (utilizing general oil-based ink cleaning solvents such as light oil) of its printing ink inferior.
In addition, when aliphatics monobasic acid and/or alicyclic monacid usage rate surpass 80 quality %, the softening temperature step-down of gained vibrin, the ultra-violet solidified reduction of the printing ink that cooperates it to obtain, thereby undesirable.
In addition, as above-mentioned vibrin, weight average molecular weight is suitable in the scope of 2000-50000, the material that more preferably has the weight average molecular weight in the 5000-45000 scope.
That is, weight average molecular weight is lower than at 2000 o'clock, and pigment-dispersing is poor, and the printing adaptability of the printing ink that obtains with it is inferior, in addition, ultra-violet solidifiedly also is tending towards inferior.On the other hand, the molecular weight of vibrin is big more, use it ultra-violet solidified printing ink ultra-violet solidified, fly China ink and the emulsification suitability all is improved, but surpass at 50000 o'clock, be difficult to handle, in addition, cause the expense of reactive diluent to increase, and then, make the tunicle rerum natura after the ultraviolet curing become inferior, so undesirable.
As above-mentioned monobasic acid, alicyclic monobasic acids such as rosin, staybelite are for example arranged; Lauric acid, stearic acid, from the aliphatics monobasic acids such as lipid acid of vegetables oil; M-nitro benzoic acid, to aromatic series monobasic acids such as tertiary butyl M-nitro benzoic acid etc.
In addition, as above-mentioned polyhydric acid, terephthalic acid, m-phthalic acid, phthalic acid (acid anhydride), trimellitic acid (acid anhydride), pyromellitic acid (acid anhydride), 2 are for example arranged, 6-naphthalene dicarboxylic acids, succsinic acid, hexanodioic acid, nonane diacid, sebacic acid, dodecanedioic acid, 1,4-cyclohexane dicarboxylic acid or hexahydrophthalic acid (acid anhydride) etc., unquestionable, these acids can use separately, also can merge use more than 2 kinds.
On the other hand, as above-mentioned multivalence alcohol, ethylene glycol is for example arranged, propylene glycol, 1, the 3-butyleneglycol, 1, the 4-butyleneglycol, 1, the 5-pentanediol, 2,2,4-trimethylammonium-1, the 3-pentanediol, 1, the 6-hexylene glycol, neopentyl glycol, glycol ether, triglycol, dipropylene glycol or tripropylene glycol etc., and weight average molecular weight is 1 of a 200-4000 scope in addition, the 4-butyleneglycol, or 1, the 4-cyclohexanediol, the oxyethane of dihydroxyphenyl propane or propylene oxide adduct, the oxyethane of hydrogenation dihydroxyphenyl propane or propylene oxide adduct, 1,4 cyclohexane dimethanol, glycerine, trimethylolethane, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol or Sorbitol Powder etc.Undoubtedly, these multivalence alcohols can use separately, also can merge use more than 2 kinds.
Vibrin with above-mentioned ultra-violet solidified monomer dilution, is made thickness varnish and is used in printing oil proportion after vibrin is made.The monomer amount of dilution needs only the varnish range of viscosities that is suitable for handling in formation, does not have particular restriction, preferably uses in the scope of 20-200 quality % with respect to vibrin.
Above-mentioned vibrin and then ultra-violet solidified in order to improve, available isocyanate compound carries out modification.As representational isocyanate compound, the aromatic diisocyanate of tolylene diisocyanate, diphenylmethanediisocyanate or Xylene Diisocyanate is arranged; The aliphatic diisocyanate of tetramethylene diisocyanate, two isocyanic acids, six methylene esters or trimethyl cyclohexane vulcabond; Or isophorone diisocyanate, methylcyclohexane-2,4-(or 2,6)-vulcabond, 4,4 '-methylene-bis (cyclohexyl isocyanate) or 1, the alicyclic diisocyanate class of 3-two (isocyanic ester methyl) hexanaphthene, the perhaps biuret body of the adducts of these each diisocyanates and multivalence alcohol and water etc., and then, polyisocyanate compounds classes such as above-mentioned various diisocyanates multipolymer each other etc. can be used wherein any.
As the consumption of isocyanate compound, the ratio of the isocyanate group (NCO) in hydroxyl in this vibrin (OH) and the isocyanate compound is preferably in the scope of OH/NCO=1/0.05-1/0.9, more preferably in the scope of 1/0.1-1/0.7.
Greater than 1/0.05 o'clock to no effect, too high less than 1/0.9 o'clock viscosity, be not suitable for.
As above-mentioned petroleum resin, can use C5 through-stone oleo-resinous, C9 through-stone oleo-resinous.Any resin in these all can obtain effect, but resin softening point is keeping important aspect the ultra-violet solidified printing ink of gained ultra-violet solidified more than 80 ℃.And softening temperature is more preferably more than 120 ℃, and preferred 140-170 ℃ petroleum resin especially are because improved the printing ink after the ultraviolet curing by film toughness, so effectively.
As above-mentioned rosin ester resin, can exemplify following several:
1) the modified rosin ester resin that forms by the condenses of polyhydric acid such as rosin and maleic anhydride, fumaric acid and multivalence alcohol;
2) rosin ester resin that forms by the condenses of multivalence alcohol such as rosin and glycerine, tetramethylolmethane, TriMethylolPropane(TMP);
3) rosin ester resin that forms by the condenses of polymerized rosin and multivalence alcohol, or the like.
Use any resin in these all can obtain effect, wherein preferably acid number is the toxilic acid modified rosin ester resin of 20-40.And resin softening point is keeping important aspect the ultra-violet solidified printing ink of gained ultra-violet solidified more than 80 ℃.But, generally remaining during in rosin ester resin much from the rosiny unsaturated group, because cause the gelation of ultra-violet solidified printing ink sometimes, so select ageing stability is not had the resin of influence.
In order in printing oil proportion, to use above-mentioned petroleum resin, rosin ester resin, when carrying out varnish, can make resin in the heating for dissolving in above-mentioned ultra-violet solidified monomer of the temperature more than the softening temperature.Resin and monomeric mixture ratio do not have particular restriction as long as in the varnish range of viscosities that formation is suitable for handling, and with respect to resin, preferably use in 100-200 quality % scope.
The softening temperature of used resin is high more, uses its solidified nature of ultra-violet solidified printing ink good more, but is difficult to dissolve in monomer, is difficult to carry out varnishization.
When using high softening-point resins such as above-mentioned petroleum resin, rosin ester resin to adjust this varnish, after this resin heating, being molten to more than the softening temperature, add in the ultra-violet solidified monomeric manufacture method, monomer is exposed under the high temperature for a long time, has the danger that causes gelation because of thermopolymerization.Even without gelation, later storage stability also reduces.
As the method for avoiding this type of problem, following manufacture method is arranged, that is, by in advance with resin dissolves in Photoepolymerizationinitiater initiater, plasticizer, thereby make said composition be in molten state under than the low temperature of this resin softening point, low temperature adds ultra-violet solidified monomer down.If this method of employing can be adjusted varnish, can not cause the reduction of monomeric gelation or varnish storage stability.
In this method, the Photoepolymerizationinitiater initiater that uses when adjusting varnish can use commercially available Photoepolymerizationinitiater initiater.The example of such photocuring polymerization initiator has Irugakiua369, Irugakiua907, Irugakiua651, Irugakiua184 (above by CIBASpesiartieChemicals society system); Kayakiua-DETX, Kayakiua-ITX (above) by Japanese chemical drug society system; O-benzoyl base M-nitro benzoic acid methyl esters; 4,4 '-diethylamino benzophenone, st-yrax, benzoin ether etc., these can use separately, or are used in combination more than 2 kinds.In addition, as sensitive agent with Photoepolymerizationinitiater initiater, also can and with 2 ethyl hexylamine, to fatty acid amine, aromatic amines such as dimethylamino ethyl benzoates.
These trigger for optical solidification, sensitive agent can use with the ratio of 0.5-20 quality % in the final printing ink that proportioning varnish obtains.
Different usually, when addition was very few, the solidified nature of printing-ink became insufficient to the addition of light trigger and sensitive agent and different with their efficiency of initiation, as one of effect of the present invention, Zong the processing that does not promptly have to eliminate can not obtain.In addition, add the above amount of requirement, owing to can increase the cost of printing-ink material, thereby undesirable.
As the plasticizer that in the varnish of above-mentioned manufacture method, uses, it is that plasticizer, phosphoric acid ester are plasticizer etc. that dihydric acid is arranged, so long as with ultra-violet solidified printing ink of the present invention in the ultra-violet solidified monomer that uses and solid resin mixes and the material low to the impregnability of printing press rubber rollers, just preferred the use.Wherein, after ultraviolet curing, do not reduce printing ink by the consideration of the viewpoint of film toughness, preferably dioctyl sebacate.
In the varnish manufacture method of above-mentioned use high softening point resin, can use above-mentioned vibrin to substitute polymerization starter or plasticizer.At this moment, the heating of high softening-point petroleum resin is dissolved in the vibrin, subsequently, in the scope that does not make resin solidification, with this resin compound cooling of even fused, adds ultra-violet solidified monomer under lower temperature, varnish is made in dilution.
According to above-mentioned manufacture method, do not need to use plasticizer and essential above polymerization starter to dissolve the petroleum resin of high softening-point.Thus, plasticizer and necessary above polymerization starter just can not remain in the printing ink yet, thereby have improved the curing tunicle rerum natura of the ultra-violet solidified printing ink of gained.In addition, also suppressed to soak into the swelling of the printer roller of elastomeric material initiation because of superfluous polymerization starter.In addition, at the ultra-violet solidified transparent varnish of chromatography on this printing-ink continuously, carry out in the printing process of ultraviolet curing, the total elimination (gloss is subdued, gloss reduce) because of the insufficient initiation of substrate ink solidification can not take place, thereby gloss, the good print of wear-resisting wiping are provided.
To mix monomer and the resin that uses among the present invention, it is more than 4 that the ultra-violet solidified printing ink that heating for dissolving obtains is adjusted to normal hexane tolerance value with varnish.
Wherein, said normal hexane tolerance value is to estimate the oil loving index of varnish, and the method for record is measured among the concrete available embodiment 1.This numerical value is big more, and the lipophilicity of its varnish is high more, and is also big more to the solvability of non-polar solvent.
Contain normal hexane tolerance value and adjust to the ultra-violet solidified printing ink of the present invention of the varnish more than 4, because the lipophilicity of printing ink self uprises, so on offset printing press when printing ink and dumping processing solution emulsification, can stable maintenance present the emulsified state of good printing adaptability.In addition, has the appropriateness flowability that good pigment wettability produces.And then the printing ink that is used in combination above-mentioned 2 kinds of resins seldom produces on printer roller and flies China ink, has greatly improved the transitivity and the emulsification adaptability of printing ink.
Simultaneously, improved this printing ink, also improved the intensity of ink solidification tunicle being printed the anchorage of substrate material.In addition, the ultra-violet solidified printing ink that contains above this varnish of 25 quality % diminishes to the impregnability of the polar rubber material that offset press uses, available general oil-based ink washs with washing composition simultaneously, can directly use the printing of oil-based ink with printing press material, printing plate material.
For ultra-violet solidified printing ink of the present invention, except above-mentioned varnish,, also can suitably add ultra-violet solidified monomer or the resin that uses in the general ultra-violet solidified printing ink for solidified nature or the viscosity of adjusting printing ink.But, the immiscible ultra-violet solidified monomer and the addition of prepolymer in normal hexane, preferably their total content is below the 30 quality % in printing ink.Add the ultra-violet solidified printing ink that surpasses 30 quality % and can damage lipophilicity, can not fully obtain effect of the present invention.
As above-mentioned ultra-violet solidified monomer immiscible in normal hexane, polyoxyethylene Viscoat 295, dipentaerythritol acrylate, two trimethylolpropane tetra-acrylate etc. are for example arranged.
In addition, the ultra-violet solidified prepolymer as immiscible in normal hexane for example has epoxy acrylate, urethane acrylate, polyester acrylate etc.
As other printing ink constituents among the present invention, the material that uses in the ultra-violet solidified printing ink before can suitably using.Its example is as follows.
1) Photoepolymerizationinitiater initiater and sensitive agent;
2) tinting material, viscosity modifier or extenders such as pigment dyestuff, mineral dye, inorganic physique plastics;
3) agent is forbidden in the polymerization that is used to pay printing ink ageing stabilities such as quinhydrones;
4) be used to adjust the adaptive tensio-active agent of ink printing, be used to prevent the phosphoric acid salt of forme sense esterification;
5) wax etc. adjustment is solidified the auxiliary agent of tunicle surface physical property.
As having good printing adaptability of oil-based ink and easily processing property simultaneously and utilizing ultraviolet curing exsiccant printing process at short notice, at commercial extensive enforcement printing oil-based ink, before this ink setting, behind the continuous chromatography transparent varnish, carry out uviolizing exsiccant method again.
Ultra-violet solidified printing ink of the present invention has the light oil detergency, detergent washing machine material, plate that available oil-based ink is used, thereby can directly use oil-based ink to print with printing press material, plate.Therefore, in above-mentioned printing process, ultra-violet solidified printing ink of the present invention does not damage the good print adaptability and easily processing property of oil-based ink, can replace oil-based ink to use.
In the method, since the moment ultraviolet curing of the ultra-violet solidified printing ink of substrate, thus total elimination such when using oxypolymerization drying type oil-based ink can not caused, in addition, wear-resisting wiping after the printing is also good, thereby can obtain the print of high gloss with very high productivity.
In order to obtain print of the present invention, the ultra-violet solidified chromatography varnish of chromatography so long as the general ultraviolet curing varnish that uses can use, wherein, the ultraviolet curing varnish used of oil-based ink preferably.As spendable ultraviolet curing varnish, the Clear coating varnish class that has the coating device that uses Diekiuainline offset OP varnish, Diekiua WLOP varnish H, Diekiua RXOP varnish (above) to wait OP varnish class, use that printing device carries out chromatography on DiekiuaclearYW3201sp, Diekiuaclear YW3205, Diekiuaclear UV1217, DiekiuaclearUV1212HP etc. (above) printing device, to connect to carry out chromatography by big Japanese ink chemical industry society system by big Japanese ink chemical industry society system.The ultra-violet solidified OP varnish of chromatography is usually with 1.5-2.5g/m
2Glue spread, Clear coating varnish is usually with 3.0-10g/m
2The glue spread chromatography after, use UV-lamp to make it to solidify, obtain desired print.
In addition, as the chromatography varnish that uses in the aforesaid method, also can use aqueous transparent varnish, the heat of utilizing UV-lamp to produce simultaneously makes water varnish ultraviolet ray dry and that utilize this lamp to send carry out ultraviolet curing to the substrate printing-ink, obtains print.
The print that obtains like this is with on oxypolymerization drying type oil-based ink, before this ink setting continuously behind the chromatography water varnish, print difference with infrared ray radiation and/or warm air drying, because substrate printing ink fully solidifies, so just can enter back operation folding or that cut off after the printing, thereby can significantly improve the productivity that print is made.
In order to obtain print of the present invention,, HYDLITH (HYDLITH) P4036 of big Japanese ink chemical industry system is for example arranged, but be not limited to this as the water varnish of chromatography.
In addition, as mentioned above, when this printing-ink is used with transparent varnish with chromatography because surface physical properties such as the drying property of print, wear-resisting wiping depend on chromatography varnish mostly, thereby can make printing-ink ultra-violet solidifiedly be necessary inferior limit.Therefore, in order to obtain the employed ultra-violet solidified printing ink of the present invention of print of the present invention, compare with common ultra-violet solidified printing ink, because the addition of Photoepolymerizationinitiater initiater is few, so can reduce generation or flavescence from the foul smell of Photoepolymerizationinitiater initiater.
On the other hand, ultra-violet solidified printing ink of the present invention can be not and transparent varnish and usefulness yet, and use separately.At this moment, be purpose to pay wear-resisting wiping, can add the wax class, perhaps, change the addition or the kind of initiator in order to obtain necessary solidified nature, adjust printing ink.
Embodiment
Below illustrate in greater detail the present invention, but the present invention is not limited by these embodiment with embodiment and comparative example.Part and % in the example are benchmark with the quality.
In this specification sheets, normal hexane tolerance value representation is measured 2g varnish and 2g toluene in beaker, be modulated into the toluene solution of varnish after, this solution is carried out titration with normal hexane, the titer (ml) of needed normal hexane when this solution forms white turbid liquid.
At first, as the reference data, that various ultra-violet solidified monomers are as shown in table 1 with 1 to 1 (mass ratio) intermiscibility when mixing with normal hexane.
The intermiscibility of table 1 Acrylic Acid Monomer and normal hexane
| Intermiscibility | ||
| 1 | Oxyethane addition (average 3 moles) Viscoat 295 | × |
| 2 | Propylene oxide addition (average 3 moles) Viscoat 295 | ○ |
| 3 | Propylene oxide addition (average 6 moles) Viscoat 295 | ○ |
| 4 | Propylene oxide addition (average 3 moles) glycerol tri-acrylate | △ |
| 5 | Two trimethylolpropane tetra-acrylate | × |
| 6 | Dipentaerythritol acrylate | × |
The explanation of numbering in the table 1:
1:Photomer4149 (Sannopuco society system)
2:Aronicks M310 (the synthetic society in East Asia system)
3:Aronicks M320 (the synthetic society in East Asia system)
4:OTA480 (DiecerUsiebi society system)
5:Aronicks M408 (the synthetic society in East Asia system)
6:Aronicks M402 (the synthetic society in East Asia system)
(A) manufacturing of resin for printing ink varnish
The modulator approach of the varnish that uses among the embodiment at first, is shown.Below, " part " and " % ", short of special pointing out all is benchmark with the quality.
(1) manufacturing of resin for printing ink varnish 1
In the presence of rare gas element, with 20 parts of neopentyl glycol, 200 parts of tetramethylolmethanes, 25 parts of hexanodioic acids, 180 parts of m-phthalic acids, 350 parts of Oleum Cocois resin acids, 225 parts of M-nitro benzoic acids 210 ℃ of heating 8 hours down, obtain the solids component acid number and be 9.1 and weight average molecular weight be 13000 vibrin.65 parts of these polyester are blended into 35 parts of Aronicks M320 (propylene oxide (average 6 moles) addition Viscoat 295, the synthetic society in East Asia system) in, 100 ℃ of following heating for dissolving 2 hours obtain the resinous varnish 1 that uses in the ultra-violet solidified printing ink of the present invention.
The normal hexane tolerance value of this varnish 1 is 12.1.
(2) manufacturing of resin for printing ink varnish 2
50 parts of Neopolymer 140 (C9 through-stone oleo-resinous of in 4 mouthfuls of flasks that stirrer, thermometer are installed, packing into; Japan petroleum chemistry society system), 7 parts of dioctyl sebacate (DOS; plasticizer; big eight chemical industry society systems) and 7 parts of OBM-100 (benzoyl methyl benzoate, Photoepolymerizationinitiater initiater, DiecerUsiebi society system); the limit feeds nitrogen; the limit was warmed up to 150 ℃ in 1 hour, heated 1 hour down at 150 ℃ again, obtained the homogeneous solution that is formed by this resin, DOS and OBM-100.Subsequently, after being cooled to 120 ℃, add 0.1 part of Q-1301 (N-nitroso-group phenyl azanol aluminium salt, agent is forbidden in polymerization, with the pure medicine of light society system), bubbling air on one side again is Yi Bian add 36 parts of Aronicks M310 (propylene oxide (average 3 moles) addition Viscoat 295, the synthetic society in East Asia system), obtain the resinous varnish 2 that uses in the ultra-violet solidified printing ink of the present invention.
The normal hexane tolerance value of this varnish 2 is 10.3.
(3) manufacturing of resin for printing ink varnish 3
50 parts of Biecasite 1110 (the toxilic acid modified rosin esters of in 4 mouthfuls of flasks that stirrer, thermometer are installed, packing into, big Japanese ink chemistry society system) and 4 parts of Irugakiua651 (benzyl dimethyl ketal, agent is forbidden in polymerization, CIBASpesiartieChemicals society system), feed nitrogen on one side, be warmed up to 120 ℃ on one side in 1 hour, reheat 1 hour obtains the homogeneous solution that is formed by this resin and Irugakiua651.To wherein adding 0.1 part of Q-1301 (N-nitroso-group phenyl azanol aluminium salt, agent and the pure medicine of light society system are forbidden in polymerization), bubbling air on one side again, add 46 parts of M-310 (the synthetic society in East Asia system) on one side, obtain the resinous varnish 3 that uses in the ultra-violet solidified printing ink of the present invention.
The normal hexane tolerance value of this varnish 3 is 5.4.
(4) manufacturing of resin for printing ink varnish 4
In the presence of rare gas element, with 20 parts of neopentyl glycol, 190 parts of tetramethylolmethanes, 25 parts of hexanodioic acids, 165 parts of m-phthalic acids, 450 parts of coco-nut oil fatty acids, 150 parts of M-nitro benzoic acids 210 ℃ of heating 8 hours down, obtain the solids component acid number and be 9.8 and weight average molecular weight be 12000 vibrin.
Then, with 35 parts of these polyester and 35 parts of Neopolymer 140 (petroleum resin, Japan petroleum chemistry society system) 180 ℃ of following heating and melting 1 hour, be blended into subsequently among 30 parts of Aronicks M320 (the synthetic society in East Asia system), 100 ℃ of following heating for dissolving 2 hours, add 0.6 part of tolylene diisocyanate again, 80 ℃ of down reactions 3 hours, thus obtain the resinous varnish 4 that uses in the ultra-violet solidified printing ink of the present invention.
The normal hexane tolerance value of this varnish 4 is 30.0.
(5) manufacturing of resin for printing ink varnish 5
The manufacture method of the resinous varnish that uses in ultra-violet solidified printing ink in general Cardboard Paper printing before below showing.With the printing ink that uses this varnish as a comparative example 1.
In the presence of rare gas element, with 20 parts of neopentyl glycol, 240 parts of tetramethylolmethanes, 25 parts of hexanodioic acids, 225 parts of m-phthalic acids, 490 parts of M-nitro benzoic acids 210 ℃ of heating 6 hours down, obtain the solids component acid number and be 9.5 and weight average molecular weight be 18000 vibrin.
Then, with 40 parts of these polyester, 30 parts of Aronicks M402 (dipentaerythritol acrylates, society's system is synthesized in East Asia) and 30 parts of Aronicks M408 (two trimethylolpropane tetra-acrylate, the synthetic society in East Asia system) 140 ℃ of following heating and melting 2 hours, add 1.0 parts of tolylene diisocyanates again, 800 ℃ of down reactions 3 hours, thus the resinous varnish 5 that uses in the printing ink of comparative example 1 obtained.
The normal hexane tolerance value of this varnish 5 is 1.3.
(B) manufacturing of the printing ink of use resinous varnish
Embodiment 1
Use resin for printing ink varnish 1, agent etc. is forbidden in hybrid pigment, Photoepolymerizationinitiater initiater and polymerization, grinds with 3 rollers, obtains being processed into the ultra-violet solidified printing ink of the present invention of 4 looks (yellow, red, blue, black).Printing oil proportion is as shown in table 2.
The printing oil proportion of table 2 embodiment 1
The explanation of table 2
The pigment that uses: Simura Fast Yellow 4320 (big Japanese ink chemical industry society system), carmine 6B971 (the society's system of refining big day), blue FR7072 (Beaeesephdiapan society system), Raben1060 (Coronbia society system), Neorit SA300 (lapicide's industry society system in vain), Hyphylar#12 (loose village industry society system)
Wax: Rubacks 2191 (Japanese smart wax society system)
Photoepolymerizationinitiater initiater: Irugakiua907 (CIBASpesiartieChemicals society system), Narkiua CS (double width chemistry society system), Kayakiua-DETX-S (Japanese chemical drug society system)
Photopolymerization monomer: Aronicks M408 (big Japanese ink chemical industry society system), AronicksM320 (the synthetic society in East Asia system), Photomer4149 (Sannopuco society system)
Agent is forbidden in polymerization: Q1301 (with the pure medicine of light society system)
Embodiment 2-4, comparative example 1
Except using resin for printing ink varnish 2-5, adopt the method the same with embodiment 1, obtain being processed into the ultra-violet solidified printing ink of the present invention and the comparative example printing ink of 4 kinds of colors.Wherein, the proportioning of blue color ink is as shown in table 3.
The printing oil proportion of table 3 embodiment 1-4, comparative example 1 (blue color ink)
(C) evaluation of physical property of gained printing ink
Printing ink (the Huang of 4 kinds of colors is processed in use, red, blue, black), UV irradiation equipment (120W is being installed, 3 of metal halide lamps) on the single paper printing press of the system R704 of Rorand society, (57.5kg/A is complete with the OK face coat, Oji Paper society system) carry out 3000 printings with 8000/hour speed after, carry out various adaptive comparison tests, promptly, (1) water yield scale value is wide, (2) swelling of rubber rollers blanket, (3) delay of printing ink pair of rollers, (4) use the detergency of oil-based ink with solvent, (5) the wear-resisting wiping of the print of a printing-ink, (6) the print gloss of coating ultraviolet curing varnish (when causing total elimination, this value diminishes) on printing ink, (7) the wear-resisting wiping of print of coating ultraviolet curing varnish on printing ink, (8) the print drying property of coating water varnish on printing ink.The results are shown in table 4.
Comparative example 2
As the example of the general printing ink of the oxidation drying type of selling on the current market, use Cartonserph (big Japanese ink chemical industry society system rapid-drying properties printing ink), carry out the evaluation the same with embodiment, the results are shown in table 4.
The printing adaptability evaluation of the various printing ink of table 4
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 | |
| (1) water yield scale value is wide | ○ | △ | ○ | ◎ | △ | ◎ |
| (2) rubber rubber cloth swelling | ○ | △ | △ | ○ | × | ◎ |
| (3) delay of pair of rollers | ○ | △ | ○ | ○ | △ | ○ |
| (4) oil-based solvent detergency | ○ | ○ | △ | ◎ | × | ◎ |
| (5) print rub resistance | ○ | △ | △ | ○ | ◎ | × |
| Gloss when (6) UV varnish uses | 75 | 70 | 65 | 80 | 80 | 40 |
| Rub resistance when (7) UV varnish uses | ◎ | ◎ | ○ | ◎ | ◎ | △ |
| Drying property when (8) water varnish uses | ◎ | ◎ | ○ | ◎ | ◎ | △ |
The expression of evaluation result: ◎ (very outstanding), zero (outstanding), △ (generally), * (poor).
Ultraviolet curing varnish: Diekiuaclear UV1212HP (big Japanese ink chemical industry system)
Water varnish: HYDLITH P4036 (big Japanese ink chemical industry system)
(1) in the offset machine, during the hypervolia of supply, is accompanied by the excessive emulsification of printing ink, produces living reduction of concentration or printing ink and the water clavate is become problems such as delay.Otherwise, when the water yield is very few, can produces on the print and pollute, thus the wide more printing ink of water yield scale value, easy more printing.
(2) (3) estimate the swelling of rubber, the delay of printing ink by the finger contact.
(4) detect by an unaided eye when estimating this machine of washing the easy degree that adopts oil-based ink to come off from roller, forme with washing composition printing ink.
(5) after (7) printing through after 2 hours, estimate by learning vibration shape frictional type fastness test machine (loading 500g, reciprocal 200 times, with good quality paper wiping print).
(6) after the printing through after 24 hours, use in the village 60 ° of-60 ° of reflectance gloss meters of color institute system to estimate print gloss.
(8) estimate just by the drying property after the UV-lamp with the finger contact.
Ultra-violet solidified printing ink of the present invention has the characteristic of the good printing adaptability of oil-based ink and easily processing property and moment ultraviolet curing, promptly uses the printing press of general oil-based ink with rubber rollers is housed, and also can print well.
In addition, at the bright varnish of printing-ink upper joint sleeve printthrough, carry out in the printing process of ultraviolet curing, good printing adaptability of oil-based ink and different processing have been kept, the total elimination when having overcome the use oil-based ink simultaneously and the problem of heavy-metal residual, productivity is better, and gloss, the good print of wear-resisting wiping are provided.
Claims (8)
1. ultra-violet solidified printing ink, it is characterized in that, contain varnish, this varnish has: the ultra-violet solidified monomer that mixes with normal hexane and in this monomer the dissolved resin, the described ultra-violet solidified monomer that mixes with normal hexane is multifunctional (methyl) acrylate with polyoxyalkylene block.
2. ultra-violet solidified printing ink according to claim 1 is characterized in that, the normal hexane tolerance value of described varnish is more than 4.
3. ultra-violet solidified printing ink according to claim 1 is characterized in that, total amount of immiscible ultra-violet solidified monomer and prepolymer is below 30% in normal hexane.
4. ultra-violet solidified printing ink according to claim 1, it is characterized in that, the vibrin that described resin is to use monobasic acid, polyhydric acid and multivalence alcohol to obtain, in the raw material when synthetic this resin, the shared ratio of aliphatics monobasic acid and/or alicyclic monobasic acid is in the scope of 15-80 quality %.
5. ultra-violet solidified printing ink according to claim 1 is characterized in that described resin is petroleum resin.
6. ultra-violet solidified printing ink according to claim 1, it is characterized in that, described resin is the mixture of vibrin and petroleum resin, the vibrin that this vibrin is to use monobasic acid, polyhydric acid and multivalence alcohol to obtain, in the raw material when synthetic this vibrin, the shared ratio of aliphatics monobasic acid and/or alicyclic monobasic acid is in the scope of 15-80 quality %.
7. print, it is characterized in that, be that each described ultra-violet solidified printing ink prints among the claim 1-6 by using, and before this ultra-violet solidified ink solidification continuously behind the ultra-violet solidified transparent varnish of chromatography, the uviolizing by UV-lamp is solidified ultra-violet solidified printing ink and transparent varnish and is obtained.
8. print, it is characterized in that, be that each described ultra-violet solidified printing ink prints among the claim 1-6 by using, and before this ultra-violet solidified ink solidification continuous chromatography aqueous transparent varnish, when the heat of utilizing UV-lamp to produce was come dry water varnish, the ultraviolet ray that utilizes same lamp to produce was carried out ultraviolet curing to the ultra-violet solidified printing ink of substrate and is obtained.
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| CN101817267B (en) * | 2009-12-11 | 2012-06-13 | 宇龙计算机通信科技(深圳)有限公司 | Printing method and device for overlapping printing ink on different bottom colors |
| CN103804988A (en) * | 2013-10-30 | 2014-05-21 | 合肥市华美光电科技有限公司 | Heat-resistant and oxidation-resistant printing ink and preparation method thereof |
| CN106046334A (en) * | 2016-06-06 | 2016-10-26 | 上海飞亚油墨有限公司 | Photocured alkyd resin for UV offset ink and preparation method of photocured alkyd resin |
| CN106046335A (en) * | 2016-06-06 | 2016-10-26 | 上海飞亚油墨有限公司 | Photocured rosin-based polyester resin for UV offset ink and preparation method of photocured rosin-based polyester resin |
| JP6378720B2 (en) * | 2016-07-26 | 2018-08-22 | ハリマ化成株式会社 | Active energy ray curable ink resin, active energy ray curable ink composition, active energy ray curable ink and cured film |
| JP7281317B2 (en) * | 2019-03-22 | 2023-05-25 | サカタインクス株式会社 | Actinic energy ray-curable ink composition, method for producing the same, and method for producing printed matter using the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0656946A (en) * | 1992-08-07 | 1994-03-01 | Dainippon Ink & Chem Inc | Ultraviolet-curing nonaqueous resin dispersion and ultraviolet-curing liquid developer |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0656946A (en) * | 1992-08-07 | 1994-03-01 | Dainippon Ink & Chem Inc | Ultraviolet-curing nonaqueous resin dispersion and ultraviolet-curing liquid developer |
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