CN1289806A - Water-in-oil emulsified ink for porous printing - Google Patents
Water-in-oil emulsified ink for porous printing Download PDFInfo
- Publication number
- CN1289806A CN1289806A CN00126352A CN00126352A CN1289806A CN 1289806 A CN1289806 A CN 1289806A CN 00126352 A CN00126352 A CN 00126352A CN 00126352 A CN00126352 A CN 00126352A CN 1289806 A CN1289806 A CN 1289806A
- Authority
- CN
- China
- Prior art keywords
- oil
- water
- printing
- oil phase
- ink
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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Landscapes
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
To provide a water-in-oil emulsion ink for stencil printing which causes little staining at roller traces, strike-through and blur and shows an excellent shelf stability, set-off preventing property, etc. The water-in-oil emulsion ink for stencil printing has a Casson plastic viscosity at 23 deg.C of <=0.4 (Pa.s) preferably <=0.2 (Pa.s), more preferably <=0.15 (Pa.s)} and preferably has a Casson yield value at 23 deg.C in an oil phase of >=0.3 (Pa).
Description
The present invention relates to emulsified ink for porous printing, in detail, relate to the roller mark pollute few, ink bleed, soak into few, and good water-in-oil emulsified ink for porous printing such as storage stability, anti-print through.
As everyone knows, stencil printing method is to use the porous printing body paper, by the perforated portion of this body paper, with printing ink from a sidesway of body paper to opposite side, print being printed on the thing surface of paper etc.
The printing ink of Shi Yonging was the emulsified ink of water-in-oil-type in the past, was to be made of volatile solvent, nonvolatile solvent, resin, tinting material, tensio-active agent, water, frostproofer, ionogen, sanitas etc.
In recent years, wheel changes porous printer also by realization automatizations such as microcomputers, and it is simple that operation becoming, and thereupon, enlarged the application of porous printing., the drying of porous printing is only soaked into drying and evaporation drying, in addition, can not use reaction resin, so that printing ink does not solidify on printing press, consider that from environmental problem the requirement of the increase in demand of two-face printing, two-face printing is at short notice also increased., when printing the inside immediately behind the surface printing, the roller of not dried lip-deep ink pollution paper feeding sticks in this greasy dirt on the print, makes print pollute (pollution of roller mark).
Before this,, open flat 8-73795 communique the spy and disclose,,, improve set-off, decide solidity by median size, the surface-area of regulation as the carbon black of the coloring components in the oil phase for set-off about the drying of printing ink.Be meant after printing just in this said set-off, when print is overlapping, the back side that not dried printing ink moves on to top print pollutes (set-off), and the print quality is reduced, and has polluted into problem for the roller mark of the two-face printing of short period of time.
In addition, Te Kaiping 7-188598 communique discloses, by contain the water-insoluble tinting material at aqueous phase, prevent infiltration, print through and improved drying property, but in the method, in the inside that is printed thing of impregnating oil phase composition, can not soak into the water-phase component that contains the water-insoluble tinting material, and being printed a lot of water-insoluble tinting materials of thing remained on surface, the roller mark pollution problem for the two-face printing that constitutes the short period of time can not get abundant effect.
Therefore, the invention reside in the shortcoming of having removed above-mentioned conventional art, it is few to provide the roller mark to pollute, and print through, infiltration are few, and good emulsified ink for porous printing such as storage stability, anti-set-off.
According to the present invention, first is to provide water-in-oil emulsified ink for porous printing, it is characterized in that, by oil phase is that 10～90 weight % and water are the water-in-oil emulsified ink that 90～10 weight % constitute, contain tinting material in the above-mentioned oil phase, and above-mentioned oil phase is below 0.4 (Pa.s) 23 ℃ Carson (Casson) plastic viscosity.
Second is to provide, and according to above-mentioned first described water-in-oil emulsified ink for porous printing, wherein, above-mentioned oil phase is below 0.2 (Pa.s) Carson's plastic viscosity of 23 ℃.
Thirdly being provides, and according to above-mentioned first described water-in-oil emulsified ink for porous printing, wherein, above-mentioned oil phase is below 0.15 (Pa.s) Carson's plastic viscosity of 23 ℃.
The 4th is to provide, and according to any one described water-in-oil emulsified ink for porous printing in above-mentioned first to the 3rd, it is characterized in that above-mentioned oil phase is more than 0.3 (Pa) at Carson's yield value of 23 ℃.
The 5th is to provide, and according to any one described water-in-oil emulsified ink for porous printing in above-mentioned first to fourth, it is characterized in that containing cycloalkanes hydrocarbon system oil in above-mentioned oil phase.
The 6th is to provide a kind of water-in-oil emulsified ink for porous printing, it is characterized in that, in any one described water-in-oil emulsified ink in above-mentioned first～the 5th, the content of tensio-active agent is below the 3 weight %.
Promptly, present inventors concentrate on studies for solving above-mentioned problem, found that, because oil phase is below 0.4 (Pa.s) { preferably below 0.2 (Pa.s) Carson's plastic viscosity of 23 ℃, more preferably 0.15 (Pa.s) is following }, so polluting, the roller mark lacks, and then, oil phase is more than 0.3 (Pa) at Carson's yield value of 23 ℃, so print through, infiltration are few.In addition, contain cycloalkanes hydrocarbon system oil in its oil phase, so storage stability is better, and then the content of tensio-active agent is below the 3 weight % in the printing ink, the institute in case set-off is good, thereby finished the present invention.
It is also indeterminate that water-in-oil emulsified ink for porous printing of the present invention plays the reason of these effects, but can be by following consideration, can think that oil phase is below 0.4 (Pa.s) Carson's plastic viscosity of 23 ℃, preferably oil phase is below 0.2 (Pa.s) Carson's plastic viscosity of 23 ℃, and then more preferably oil phase is 0.15 (Pa.s) when following Carson's plastic viscosity of 23 ℃, and the low viscosity composition in the ink composition of printing back is soaked in the paper rapidly, reduced the roller mark pollutes.On the other hand, wish that oil phase is more than the 0.02Pa.s 23 ℃ plastic viscosity, preferably more than the 0.05Pa.s.When plastic viscosity during less than 0.02Pa.s, the emulsified ink viscosity is arranged, set-off is poor during printing, and is from the phenomenon of print roller leakage of oil, improper with the coupling of printing press.
In addition, by the Carson yield value of oil phase at 23 ℃ made more than 0.3 (Pa), the expansion of pigment can reduce infiltration, print through in the paper of control printing back.On the other hand, wish that oil phase is below 10 (Pa) at Carson's yield value of 23 ℃, preferably below 5 (Pa).When Carson's yield value of oil phase during greater than 10 (Pa), because the mobile variation of pigment, residual a lot of pigment on the paper surface then, so decide solidity, the remarkable variation of touch dry.
And then, owing in oil phase, contain cycloalkanes hydrocarbon system oil, can think to have the effect that does not hinder ink stability.
The effect of the content of tensio-active agent below 3 weight % can be thought and suitably weaken by the surface film intensity that makes emulsion because just the printing back accelerates to soaking into of paper, institute in case set-off improve.On the other hand, wish that the content of tensio-active agent is more than 1 weight %.This be because if the content of tensio-active agent less than 1 weight %, surface film intensity excessively a little less than, storage stability significantly is compromised.
In addition, oil phase among the present invention is 23 ℃ Carson (Casson) plastic viscosity, refer to and adopt stress mobilometer (protecting the system CSR-10 of woods (ボ-リ Application) society), at 23 ℃, in the conically shaped of 2cm2 degree, measure the flow curve of stress from 12.5Pa to 150Pa, use Carson's rough and ready formula, obtain Carson's plastic viscosity, Carson's yield value by calculating.
τ: shear-stress D: velocity of shear
τ
0: yield value Eta: plastic viscosity
Below, illustrate in greater detail the present invention.
The water of above-mentioned emulsion prevents that by water, ionogen, mould inhibitor, water evaporation agent, water-soluble polymer, oil-in-water-type resin emulsion etc. from constituting, in addition, above-mentioned oil phase is made of oil component, insoluble painted dispersion agent, insoluble tinting material, matrix pigment, resin, emulsifying agent etc.These constituents can use the known material that does not hinder emulsion to form.At aqueous phase,, also can add the dispersion agent of tinting material and tinting material for auxiliary painted purpose.
As toner used in the present invention, can use versicolor known pigment, dispersed dye etc. can be enumerated acetylene black, channel black, the carbon black class of furnace black etc., aluminium powder, the metal powder of bronze powder etc., red iron oxide, molybdenum lead, ultramarine, chromic oxide, mineral dyes such as titanium oxide, insoluble azo colour, azo lake pigment, condense the azo pigment of azo pigment etc., the phthalocyanine series pigments of metal-free phthalocyanine pigment and copper phthalocyanine pigments etc., anthraquinone system, quinoline a word used for translation ketone system, isoindoline ketone system, isoindoline is dioxazine system, the intellectual circle is that the perylene is perylene ketone system, thioindigo system, Kui phthalein ketone system, the fused polycycle series pigments of metal complex etc., the pigment dyestuff in the color lake of acidity or basic dyestuff etc., two azoic dyestuffs, the oil-soluble colourant of anthraquinone based dye etc., high-visibility pigment etc.
As high-visibility pigment, be when the synthetic resins mass polymerization or after the polymerization, dissolving or on have hair dyed the fluorescence dye of various form and aspect, with the painted block resin that obtains pulverize, miniaturization, the high-visibility pigment of so-called synthetic resins solid solution build, as the synthetic resins of carried dye, melmac, urea resin, sulfonamide resin, Synolac, vinyl chloride resin etc. are arranged, can enumerate the high-visibility pigment of carried dye in them etc.
These dye pigment class, can be independent, also can mix interpolation more than 2 kinds.
Be dispersed in the median size of the insoluble tinting material in the oil phase, hope is 10～0.1 μ m, preferably 1～0.1 μ m.
Its usage quantity can be added as required, but 2～15 weight % normally.
For carbon black, owing to be to add in the oil phase in the present invention, hope use pH is less than 5 acid carbon black.
As representational carbon black, can enumerate MA-100, MA-7, MA-77, MA-11, #40, #44 (Mitsubishi Chemical society system) Raven1100, Raven1080, Raven1255, Raven760, Raven410 (Colombia's (コ ロ Application PVC セ Application) carbon society system) etc.
Cycloalkanes hydrocarbon system oil used in the present invention can be enumerated the carbon content (C of the naphthenic hydrocarbon composition of ring analysis
N) be 30%C
NMore than, and the carbon content (C of aromatic component
A) be 20%C
ABelow, and the carbon content (C of paraffinic hydrocarbons composition
p) be 55%C
pFollowing mineral oil; Lubricating oil (モ-PVC Le) oil society adds brother's oil A Qike oil 155 and 300ID, adds its gram light oil of brother's oil Acker and adds brother's oil A Qike oil C heavy oil, and the Dai Yana of the emerging product of bright dipping society does not rein in this oil (NP-24, NR-26, NR-68, NS-90S, NM-280 etc.), Dai Renafu comes West Asia series (N-28, N-90, N-150, U-46, U-56, U-68, U-130, U-170, U-260); The third fractional oil series of Japan Sunoco society (410,420,450,480,3125,4240 etc.) etc.
Each symbolic significance of above-mentioned ring analysis value is as follows:
%C
A=aromatic series carbonatoms is for the percentage of total carbon atom number
%C
N=naphthenic carbon atomicity is for the percentage of total carbon atom number
%C
p=paraffinic carbon atomicity is for the percentage of total carbon atom number
As oil used in the present invention, except above-mentioned oil, in the scope that does not hinder storage stability, also can use other oil.For example can use oil is flux, white oil, spindle oil, machinery oil, lubricating oil, mineral oil; Toenol 1140, appropriate youngster's oil, Semen Maydis oil, sweet oil, rape seed oil, Viscotrol C, synourin oil, soybean oil, coconut wet goods vegetables oil etc.
In the present invention, in the scope that does not hinder security, storage stability, also can and use synthetic oil.
As alkane hydrocarbon system oil used in the present invention, can enumerate add the brother oil A Qike oil series (1010,1022,1032,1046,1068,1100,3032,3046,3068 etc.), the day stone high-grade oil series (B, C, D, E etc.) of Japan petroleum society, generation hot Naples oil (PX-32, PX-90, PW-32, PW-90, PW-380, PS-32, PS-90, PS-430 etc.), the Dai Renafu of the emerging product of bright dipping society of lubricating oil oil society and come West Asia series (S-32, S-90, P-32, P-90, P-150, P-180, P-430 etc.) etc.
As safe oil series solvent, can enumerate the Esso crust series (C, E, G, H, L, M etc.) of Exxon chemistry society and the AF solvent oil series (No. 4, No. 5, No. 6, No. 7) of dust gram cringle (D30, D40, D80, D110, D130 etc.) Japan petroleum society etc.
When considering the security of these oil components, wish to use the Ppolynuclear aromatic composition that contains the aromatic hydrocarbon that condenses aromatic ring more than 3 rings less than 3 quality %'s.And then, aromatic series oil that also can be safe to use (spy opens flat 11-80640 communique) as required, the natural characteristics that promptly makes a variation, index M I less than 1.0, aromatic hydrocarbons composition (%C
A) be that 20-55%, aniline point are below 100 ℃, and with oily gross weight is benchmark, benzo [a] anthracene, benzo [b] fluoranthene, benzo [j] fluoranthene, benzo [k] fluoranthene, benzo [a] perylene, dibenzo [a, j] content of Ppolynuclear aromatic of acridine etc. is respectively below 10 ppm by weight, and the total amount of content is below 50 ppm by weight.
Emulsifying agent used in the present invention is that purpose is used with the emulsion that forms water-in-oil-type, can use in anion surfactant, cats product, amphoterics, the nonionogenic tenside any a kind, as long as stability is produced effect, no matter be low molecule, polymer or and with can.Wherein, nonionogenic tenside preferably for example can be enumerated the sorbitan-fatty acid ester of sorbitan monooleate, Span-83, sorbitan trioleate, sorbitan monostearate etc.; The polyoxyethylene sorbitan fatty acid ester of polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate etc.; The polyglycerol fatty acid ester of Zerol, ten trioleins, the many monoricinoleins of six glycerine etc.; The polyoxyethylene glycerol fatty acid ester of polyoxyethylene sorbitol fatty acid ester, polyoxyethylene glycerine vegetable fatty acid esters etc.; Cithrol, Voranol EP 2001, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl amine fatty amide, polyoxyethylene polyoxy-propylene, polyoxyethylenated castor oil hardened castor oil and higher alcohols etc., separately or more than 2 kinds and usefulness, the high emulsion of preparation storage stability.Addition is 0.5-15 weight %, 1～3 weight % preferably of ink by weight normally.
In addition, in oil phase, in not hindering the scope that forms emulsion, can add dispersion agent, matrix pigment, gelating agent and the oxidation inhibitor etc. of resin, tinting material.In addition, above-mentioned emulsifying agent also can be contained in the oil phase.At aqueous phase, in the scope that does not hinder emulsion to form, can add the dispersion agent, water-soluble polymer, oil-in-water-type resin emulsion, Antisepticize and mildew preventive, water evaporation suppressor, frostproofer, pH regulator agent, electrolytic agent, matrix pigment of insoluble tinting material etc.
As the resin that adds in the oil phase, can be with rosin; The rosin series resin of polymerization rosin, hydrogenated rosins, rosin ester, rosen polyester resin, hydrogenated wood rosin glycerol ester etc.; Rosin modified alkyd resin, Abietyl modified maleic acid resin; The Abietyl modified rosin of rosin modified phenolic resin etc.; Maleic acid resin; Resol; Petroleum resin; The rubber derivative resin of thermoprene etc.; Terpine resin; Synolac; Polymerized castor oils etc. mix interpolation more than a kind or 2 kinds.As they representational resins, can enumerate the promise 353 of tower fiber crops, the promise 403 of tower fiber crops, the promise 361 of tower fiber crops, the promise 387 of tower fiber crops, the promise 340 of tower fiber crops, the promise 400 of tower fiber crops, the promise 396 of tower fiber crops, the promise 354 of tower fiber crops, KG836, the KG846 of waste river chemistry society system, the rosin modified phenolic resin of KG1834, KG1801 etc. etc.
The weight-average molecular weight of resin, from deciding solidity and printing suitability, preferably 30,000～150,000, more preferably 5.5 ten thousand～150,000, and then, these resins preferably have the resin that deliquescent tolerance value is (can mix more than the 1g No. 0 solvent) more than the 1g/g for No. 0 solvent of day stone in the 1g resin.In addition, the resin usage quantity when adding resin in oil phase is from cost and printing suitability, preferably 2～50 weight % of oil phase, more preferably 5～20 weight % of printing ink.When the weight-average molecular weight of resin is low and addition after a little while, little for the effect of deciding solidity.In addition,, resin content too high in weight-average molecular weight for a long time, produce ink viscosity uprise, from printing suitability problems such as roller rear end leakage of oils.
Synolac used in the present invention is made of grease, polyprotonic acid and polyvalent alcohol.As grease, can enumerate Oleum Cocois, plam oil, sweet oil, Viscotrol C, Rice pollard oil, cotton seed wet goods iodine number nondrying oil or semi-drying oil and their lipid acid below 80, but in the iodine number of Synolac is scope below 80, also can use siccative oil such as a part of soybean oil, oleum lini, tung oil.
As above-mentioned polyprotonic acid, can use unsaturated polyprotonic acids such as the saturated polybasic acid of phthalate anhydride, m-phthalic acid, terephthalic acid, succsinic acid, hexanodioic acid, sebacic acid, tetrahydrobenzene dioctyl phthalate etc. and toxilic acid, maleic anhydride, fumaric acid, methylene-succinic acid, citraconic anhydride.
As above-mentioned polyvalent alcohol, can make spent glycol, glycol ether, triglycol, polyoxyethylene glycol, propylene glycol, 1, ammediol, 1,4-butyleneglycol, glycerol, TriMethylolPropane(TMP), neopentyl glycol, Glycerol dimer, two triglycerols, tetramethylolmethane, Dipentaerythritol, mannitol, Sorbitol Powder etc.
The oil length of Synolac, the weight % in the resin with the lipid acid in the grease in the presence of tri-glyceride the time represents.Synolac from dispersion stabilization, and form the problems such as version copper mesh plug-hole of tunicle, preferred oil length is that 60-90, iodine number are below 80.The weight-average molecular weight of Synolac, preferably less than 30,000, more preferably below 10,000.
As the colorant dispersion that is dispersed in the tinting material in the oil phase, can use not hinder emulsion to form, also can use mentioned emulsifier with nonionogenic tenside and water-soluble polymer.
As dispersion agent, can enumerate alkylamine is macromolecular compound, the aluminum chelate based compound, phenylethylene-maleic anhydride is the copolymerized macromolecule compound, polycarboxylate type macromolecular compound, fat family polycarboxylic acid, the amine salt class of macromolecule polyester, ester type anion surfactant, the long-chain amine salt of high-molecular weight poly carboxylic acid, the salt of long-chain polyaminoamide and polymer acid polyester, polyamide-based compound, phosphoric acid ester is a tensio-active agent, alkyl sulfocarboxylic Barbiturates, the sulfonated class, dioctyl sulfo-succinic acid salt, polymine, alcohol amine salt and resin etc. with insoluble tinting material dispersion energy of Synolac etc.In addition, as long as in the scope of the storage stability that does not hinder printing ink, also can enumerate ionic surfactant, amphoterics etc.
These dispersion agents can separately or mix more than 2 kinds and add, and the addition of the colorant dispersion beyond polymer and the resin is below the 40 weight % of tinting material weight, preferably 2～35 weight %.Synolac, when adding the high-molecular weight resin, produce effect especially for the dispersion stabilization of insoluble tinting material, but Synolac separately or with the resin content of other dispersion agents and time spent,, be more than 0.05 weight part preferably with respect to insoluble tinting material 1 weight part.
Gelating agent has the resin gelization that will be contained in the oil phase, improve printing ink storage stability, decide the effect of solidity, flowability, as the gelating agent that is added in this printing ink, preferably with oil phase in resin complex bonded compound.Example as such compound, be the organic acid salt that contains metals such as Li, Na, K, Al, Ca, Co, Fe, Mn, Mg, Pb, Zn, Zr, organic chelated compound, metallic soap oligopolymer etc., can enumerate the organic chelated compound etc. of the stearate, diisopropoxy list ethyl acetoacetic acid aluminium etc. of the metallic naphthenate, Zinic stearas etc. of the sad metal-salt, manganese naphthenate etc. of aluminium octoate etc. particularly.These gelating agents can add in the oil phase more than a kind or 2 kinds, and its addition is following, 5～10% (weight) preferably of 15% (weight) of resin in the oil phase.
To be added on oxidation inhibitor in the oil phase be butylated hydroxytoluene, do not have stone propyl propionate, butyl hydroxyanisole etc., can prevent from oxidations such as binder resin in the oil phase from can prevent ink viscosity rising etc. thus by adding these materials.In addition, its addition is below the 2 weight % of oil in the printing ink, preferably 0.1～1.0% (weight).And oxidation inhibitor can separately or mix more than 2 kinds and use.
In addition, for impermeable in printing ink or adjusting viscosity, also can add matrix pigment.Can enumerate the micropartical that organic particle such as inorganic fine particles such as carclazyte, silicon oxide, talcum, clay, lime carbonate, barium sulfate, titanium oxide, alum carclazyte, diatomite, kaolin, mica, aluminium hydroxide and polyacrylic ester, urethane, polyester, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polysiloxane, resol, Resins, epoxy or their multipolymer constitute as being added on matrix pigment in the printing ink.
Can enumerate (Fengshun society of foreign firm system), TIXOGEL series (VP, DS, GB, VG, EZ-100 etc.) such as Ah dust Kiel 200, A Ailuo Kiel R972 etc. (Japanese A Ailuo Kiel society), NEW D ORBEN (white lapicide is society's system already), BEN-GEL, S-BEN, ORGANITE, POTIGEL (daily output Ka Dela catalyzer society system) etc. as the object lesson of matrix pigment.These can be added in oil phase, water or the two-phase, addition, with respect to printing ink, preferably 0.1-50 weight %, more preferably 1-5 weight %.
At the aqueous phase of emulsified ink,, also can add water-soluble polymer or oil-in-water-type resin emulsion in order to preserve moisture or tackify and insoluble tinting material, matrix dispersing of pigments and fixed consolidating.
As water-soluble polymer, can add following natural or synthetic macromolecule particularly.Natural polymers such as starch, mannosans, sodiun alginate, Polygalactan, tragcanth, gum arabic, pullulan (プ Le ラ Application), dextran, xanthene glue, gelatin, gelatin, collagen, casein for example; The semi-synthetic polymer of carboxymethyl cellulose, Walocel MT 20.000PV, methylcellulose gum, Natvosol, hydroxypropylcellulose, Vltra tears, hydroxymethyl starch, carboxymethyl starch, diethyl starch aldehyde etc.; The corrective of acrylic resin and sodium polyacrylate etc., polyethylene imide, polyvinyl alcohol, Polyvinylpyrolidone (PVP), polymine, polyacrylamide, the poly-N-alkyl-substituted acrylamide of poly-N-acryloyl tetramethyleneimine or poly N-isopropyl acrylamide etc., polyethylene oxide, polyvinyl methyl ether, styrene-maleic anhydride copolymer, the styrene-propene acid copolymer and with alkyl with they polymers of hydrophobization partly, in addition, about acrylamide polymer and acrylic acid polymer, also can be with alkyl with the substituting group polymkeric substance of the copoly type of hydrophobization partly.In addition, can use the block copolymer of polyethylene and polypropylene (Port リ ピ レ Application) or polybutene.
These water-soluble polymers can mix separately or more than 2 kinds, add being contained in below the 25 weight % of the water in the printing ink, preferably 0.5-15 weight %.
As the oil-in-water-type resin emulsion, can use synthetic macromolecule, also can use natural polymer.As polymer, can enumerate Vinyl Acetate Copolymer, polyacrylic ester, polymethacrylate, polyvinyl chloride, ethylene-vinyl acetate copolymer, vinyl acetate-acrylic copolymer, copolymer in cinnamic acrylic ester, vinylidene chloride-acrylate copolymer, vinyl chloride-vinyl acetate copolymer, polyurethane etc.As natural product, can enumerate those polymers that can be added in the oil phase etc.These are in the scope of the stability that does not hinder water-in-oil emulsified ink; also can be more than 2 kinds and usefulness, in addition, also can add dispersion agent, protective colloid, tensio-active agent as dispersing method; in addition, also can be by no soap (ソ-プ Off リ-) letex polymerization synthetic material.The minimum film temperature of making of these oil-in-water-type resin emulsions is preferably below 40 ℃.
Being added on aqueous phase is to be used for preventing in emulsion bacterium and mold propagates with Antisepticize and mildew preventive, when the prolonged preservation emulsion, wishes to add Antisepticize and mildew preventive.Its addition is to be contained in below the 3 weight % of the water in the printing ink, preferably 0.1-1.2 weight %.As Antisepticize and mildew preventive, except aromatic hydroxy compounds such as Whitfield's ointment, phenols, methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate and chlorine compound thereof, can use Sorbic Acid and dehydro-acetic acid etc., can independent or mixing use more than 2 kinds with them.
But the water evaporation prevents agent and frostproofer dual-purpose, and the medicine that adds with these purposes is the glycol of ethylene glycol, glycol ether, propylene glycol etc.; The rudimentary saturated monohydroxy alcohol of methyl alcohol, ethanol, Virahol, butanols, isopropylcarbinol etc.; Polyvalent alcohol such as glycerine and Sorbitol Powder etc.These medicines can add use more than a kind or 2 kinds, the spring addition is below the 15 weight % of the water weight in the printing ink, preferably 4～12 weight %.
The pH regulator agent that is added on aqueous phase is trolamine, sodium-acetate, triamylamine etc., in case of necessity, adds these pH regulator agent, can make the pH of water remain on 6～8.If the pH of water departs from above-mentioned scope, when the interpolation tackifier are used water-soluble polymer, there are problems such as its effect is compromised.
Adding ionogen at aqueous phase is in order to improve the storage stability of emulsion, can to use by citric acid, tartrate, SO
4, CH
3CO
2, Cl, Br, NO
3, ClO
3, the ionogen that constitutes of positively charged ions such as negatively charged ion such as I, SCN and Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Al.Therefore, as ionogen in this interpolation, preferably sal epsom, sodium sulfate, Trisodium Citrate, sodium hydrogen phosphate, Sodium Tetraborate, sodium-acetate, Tai-Ace S 150 etc., its addition are the 0.01-10 weight % of water, preferably 0.1-2 weight %, 0.5-1.5 weight % more preferably.
In addition, in water-in-oil emulsified ink for porous printing of the present invention,, printing and print roller are separated well, or roll up on the printing, can in oil phase, add paraffin in order to prevent for when printing.In addition, add trolamine or sodium hydroxide etc., can further promote owing to add the high viscosityization that water-soluble polymer causes at aqueous phase.And then, adding rust-preventive agent and defoamer at aqueous phase, printing press is because of the printing ink corrosion with prevent that printing ink from bubbling in the time of can preventing to print.These additives can add the known product that for porous printing printing ink is added as required, and its addition gets final product with the amount that product were identical in the past.
Regulate oil phase and water liquid in the same manner when emulsified ink of the present invention can prepare with emulsified ink in the past, in known mulser, the emulsification of two-phase liquid is made printing ink.That is, preparation tinting material, emulsifying agent and the abundant dispersive oil phase of additives such as resin that adds as required to wherein, add tinting material, Antisepticize and mildew preventive lentamente and add the aqueous solution of water-soluble polymer etc. as required, carry out emulsification and get final product.
By the viscosity of the also adjustable fuel-economizing China ink of agitation condition, so long as the viscosity of system just can, have no particular limits, but wish sliding velocity 20s
-1The time viscosity be 3～40Pas, 10-30Pas preferably.
Embodiment
Below, be described more specifically the present invention by embodiment, but the present invention is not subjected to the restriction of this embodiment.In addition, said part is weight part below.
Embodiment 1-4 and comparative example 1-4
＜in oil phase, contain the manufacturing of the W/O emulsified ink of insoluble tinting material 〉
Use each composition shown in table 1 and the table 2, at first,, regulate insoluble colorant dispersion with the mixing tinting material of 3 rollers, oil, insoluble colorant dispersion.This insoluble colorant dispersion (below, be called insoluble colorant dispersion) in, adding is through the varnish with tensio-active agent, oil and resin etc., make oil phase, water to formations such as wherein adding, frostproofer, antiseptic-germicide, ionogen or water soluble resins, carry out emulsification, make emulsified ink for porous printing.As required, also can add other compositions such as matrix pigment.
In addition, carbon black is to use the system RAVEN1100 of Colombia carbon society, the copper phthalein spends orchid to be to use the system Lionol Blue FG-7330 of Toyo Ink society, pigment dispersing agent is to use aginomoto society system cloth to come the special AL-M of Acker, emulsifying agent (Span-83) is to use day system SO-15 of photochemistry society, alkane hydrocarbon system oil is to use lubricating oil society system to add its gram series (1010 of brother's oil Acker, 1046,1100) alkane hydrocarbon system oil is to use lubricating oil society system to add its gram series (light oil of brother's oil Acker, 300ID), Japan Sunoco society system third fractional oil 410 is to use No. 5, the system AF of society of Nippon Mitsubishi Oil solvent as the oil series solvent.In addition, ethylene glycol, sal epsom and methyl p-hydroxybenzoate are to use commercially available product.
Embodiment: 1～4 and the prescription of comparative example 1～4 represent that respectively in table 1 and the table 2, the component list of the ring analysis of the oil that embodiment and comparative example are used is shown in the table 3.
Ring analysis of the present invention is according to P.344 (virtuous hall version can be compiled, be supported to Japanese lubrication theory) described n-d-M method enforcement of lubrication guide.In addition, stratographic analysis is according to JISK2536[petroleum product-hydrocarbon type test method] implement.
Table 1
| Embodiment | |||||
| ????1 | ????2 | ????3 | ????4 | ||
| Tinting material | Carbon black Raven1100 copper phthalein is spent orchid | ????4.7 ????0.6 | ????6.2 ????0.8 | ????6.2 ????0 | ????6.2 ????0.8 |
| Pigment dispersing agent | Aluminum chelate | ????0.3 | ????0.4 | ????0.4 | ????0.4 |
| Emulsifying agent | Sorbitol anhydride oleate | ????2.8 | ????2.5 | ????3.6 | ????2.5 |
| Oil component | (alkane hydrocarbon system mineral oil) A Qike 1010 Ah its restrain 1046 Ah its gram, 1100 (cycloalkanes hydrocarbon system mineral oil) A Qike light oil third fractional oil, 410 Ah its gram 300ID | ????21.6 | ????13 ????8.6 | ????12.8 | ????21.6 |
| The oil series solvent | AF solvent 5 | ?????6 | |||
| Oil phase adds up to | ????30 | ????31.5 | ?????29 | ????31.5 | |
| Water frostproofer ionogen sanitas | Ion-exchange water glycol sal epsom methyl p-hydroxybenzoate | ????58.9 ????10 ????1 ????0.1 | ????57.4 ????10 ????1 ????0.1 | ?????59.9 ?????10 ?????10 ?????0.1 | ????57.4 ????10 ????1 ????0.1 |
| Water adds up to | ????70 | ????68.5 | ?????71 | ????68.5 | |
Table 2
| Comparative example | |||||
| ????1 | ????2 | ????3 | ????4 | ||
| Tinting material | Carbon black Raven1100 copper phthalein is spent orchid | ????4 ????0.5 | ????4 ????0.5 | ????6.2 ????0.8 | ????4.5 ????0 |
| Pigment dispersing agent | Aluminum chelate | ????0.2 | ????0.3 | ????0.5 | ????1.0 |
| Emulsifying agent | Sorbitol anhydride oleate | ????4 | ????4 | ????2.5 | ????2.5 |
| Oil component | (alkane hydrocarbon system mineral oil) A Qike 1010 Ah its restrain 1046 Ah its gram, 1100 (cycloalkanes hydrocarbon system mineral oil) A Qike light oil third fractional oil, 410 Ah its gram 3001D | ????4 ????17.3 | ????4 ????15.2 | ????23.5 | ?????10.0 ?????17.5 |
| The oil series solvent | AF solvent 5 | ||||
| Oil phase adds up to | ?????30 | ????28 | ????33.5 | ?????35.5 | |
| Water frostproofer ionogen sanitas | Ion-exchange water glycol sal epsom methyl p-hydroxybenzoate | ?????58.9 ?????10 ?????1 ?????0.1 | ????60.9 ????10 ????1 ????0.1 | ????55.4 ????10 ????1 ????0.1 | ?????53.4 ?????10 ?????1 ?????0.1 |
| Water adds up to | ?????70 | ????72 | ????66.5 | ?????64.5 | |
Table 3
| ％C A | ?％C N | ?％C p | |
| Alkane hydrocarbon system oil A Qike 1010 Ah its restrain 1046 Ah its gram 1100 | 7 7 7 | 31 30 28 | 62 63 65 |
| Cycloalkanes hydrocarbon system oil A Qike light oil third fractional oil 410 Ah its gram 300ID | 1 10 16 | 54 47 35 | 45 43 49 |
The evaluation of＜emulsified ink 〉
Use these printing ink, fully print, print after fully entering printing ink in the printing press with commercially available society of Ricoh drilling printing machine (VT3920).
It is with behind the surface printing that the roller mark pollutes, and the degree of the pollution that the feed roll when after 1 minute the inside being printed causes is estimated.With serious pollution conduct * *, pollute few as ◎, with * *, *, 5 kinds of grades of △, zero, ◎ estimate.
Print through is with the naked eye to estimate the whole the inside of having printed, print through serious for *, fewer be zero, and * 3 kinds of grades of △ zero estimate.
Infiltration is with microscope (100 times), observes the part of having printed and the line of delimitation of printing not, infiltration is many be *, permeate fewly as △, almost do not have the conduct zero of permeating, estimate with these 3 kinds of grades.
The storage stability of printing ink is preserved under the room temperature in 1 year, separates many conducts 1, few conduct 10, estimates.
Set-off is to observe 50 the insides of printing eclipsed prints continuously, with serious pollution for *, to pollute few be zero, with *, △, 3 kinds of grades of zero estimate.
The evaluation of＜oil phase 〉
Measure the oil phase of above-mentioned prescription with strain galvanometer (the system CSR-10 of Po Lam society).About measuring, be in 23 ℃, the cone of diameter 2cm, cone angle 2 degree, measure stress to 12.5Pa～150Pa flow curve before, calculate Carson's plastic viscosity, Carson's yield value with Carson's rough and ready formula.In addition, the mensuration of flow curve is to carry out Stress Ramp by the stress lift velocity of 2pa/s to measure.
| Embodiment | Comparative example | |||||||
| ????1 | ????2 | ????3 | ????4 | ????1 | ????2 | ????3 | ????4 | |
| Oil phase plastic viscosity (Pa.s) | ?0.38 | ??0.17 | ??0.13 | ??0.15 | ??0.63 | ??0.45 | ??0.13 | ??0.35 |
| Oil phase yield value (Pa) | ?1.54 | ??1.22 | ??1.44 | ??0.97 | ??1.10 | ??0.81 | ??0.20 | ??0.05 |
| The roller mark is estimated | ??△ | ??○ | ??◎ | ??◎ | ×× | ??× | ??◎ | ??△ |
| Print through | ??○ | ??○ | ??○ | ??△ | ??△ | ??△ | ??× | ??× |
| Infiltration | ??○ | ??○ | ??○ | ??△ | ??△ | ??△ | ??× | ??× |
| Storage stability | ??4 | ??6 | ??5 | ??8 | ??4 | ??7 | ??8 | ??8 |
| Set-off | ??△ | ??○ | ??× | ??○ | ??× | ??× | ??○ | ??○ |
Can show because the oil phase of claim 1 is that 0.4 (Pas) pollutes with next pair roller mark and produce effect Carson's plastic viscosity of 23 ℃ from the embodiment 1 of table 4 and comparative example 1,2.In addition, the oil phase that shows claim 2 from embodiment 2 and embodiment 1 is 0.2 (Pas) when following Carson's plastic viscosity of 23 ℃, has the roller mark and pollutes few effect.And then the oil phase that shows claim 3 from embodiment 3,4 and embodiment 1,2 is 0.15 (Pas) when following Carson's plastic viscosity of 23 ℃, has the roller mark and pollutes still less effect.
In addition, the oil phase that shows claim 4 from embodiment 1,2,3,4 and comparative example 3,4 is 0.3 (Pa) when above at Carson's yield value of 23 ℃, has print through, effect that infiltration is few.And then, when embodiment 4 and comparative example 1 show the cycloalkanes hydrocarbon system oil that contains claim 5, have the good effect of storage stability.And then, show that from embodiment 4 and comparative example 1,2 surfactant content of claim 6 is 3 weight % when following, has the good effect of anti-set-off.
Claim 1,2 or 3 water-in-oil emulsified ink for porous printing, in oil phase, contain colouring agent, and above-mentioned oil phase is below 0.4 (Pas) Carson's plastic viscosity of 23 ℃, preferably 0.2 (Pas) following, more preferably below 0.15 (Pas), so that the roller mark pollutes is few.
The water-in-oil emulsified ink for porous printing of claim 4, oil phase is more than 0.3 (Pa) at Carson's yield value of 23 ℃, so also have print through, the few effect of infiltration.
The water-in-oil emulsified ink for porous printing of claim 5 contains cycloalkanes hydrocarbon system oil in oil phase, so also have the good effect of storage stability.
The water-in-oil emulsified ink for porous printing of claim 6, the content of surfactant are below 3 % by weight, so also have the excellent results of anti-set-off.
Claims (6)
1. water-in-oil emulsified ink for porous printing, this emulsified ink is the water-in-oil emulsified ink that is made of oil phase 10～90 weight % and water 90～10 weight %, it is characterized in that, in above-mentioned oil phase, contain tinting material, and above-mentioned oil phase is below 0.4 (Pas) Carson's plastic viscosity of 23 ℃.
2. the described water-in-oil emulsified ink for porous printing of claim 1, wherein, above-mentioned oil phase is below 0.2 (Pas) Carson's plastic viscosity of 23 ℃.
3. the described water-in-oil emulsified ink for porous printing of claim 1, wherein, above-mentioned oil phase is below 0.15 (Pas) Carson's plastic viscosity of 23 ℃
4. any 1 described water-in-oil emulsified ink for porous printing in the claim 1～3 is characterized in that above-mentioned oil phase is more than 0.3 (Pa) at Carson's yield value of 23 ℃.
5. any one described water-in-oil emulsified ink for porous printing in the claim 1～4 is characterized in that containing in the above-mentioned oil phase cycloalkanes hydrocarbon system oil.
6. water-in-oil emulsified ink for porous printing, this emulsified ink is any 1 described water-in-oil emulsified ink in the claim 1～5, the content that it is characterized in that tensio-active agent is below the 3 weight %.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27359099 | 1999-09-28 | ||
| JP273590/1999 | 1999-09-28 | ||
| JP158854/2000 | 2000-05-29 | ||
| JP2000158854A JP4050443B2 (en) | 1999-09-28 | 2000-05-29 | Water-in-oil emulsion ink for stencil printing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1289806A true CN1289806A (en) | 2001-04-04 |
| CN1205281C CN1205281C (en) | 2005-06-08 |
Family
ID=26550713
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB001263528A Expired - Lifetime CN1205281C (en) | 1999-09-28 | 2000-09-08 | Water-in-oil emulsified ink for porous printing |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4050443B2 (en) |
| CN (1) | CN1205281C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1300267C (en) * | 2004-04-20 | 2007-02-14 | 东北理光株式会社 | Emulsified ink for stencil printing |
| CN101573662B (en) * | 2006-11-06 | 2012-04-18 | 东丽株式会社 | Precursor for waterless lithographic printing plate |
| CN103666100A (en) * | 2013-12-11 | 2014-03-26 | 苏州谊恒印务有限公司 | Water-based porous plate ink |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4880832B2 (en) * | 2001-07-09 | 2012-02-22 | 東北リコー株式会社 | Emulsion ink for stencil printing |
| JP2005330461A (en) * | 2004-04-20 | 2005-12-02 | Tohoku Ricoh Co Ltd | Emulsion ink for use in stencil printing |
| JP4401914B2 (en) * | 2004-09-17 | 2010-01-20 | 株式会社リコー | Toner, method for producing the same, and image forming method |
| JP6059098B2 (en) * | 2013-07-05 | 2017-01-11 | 化研テック株式会社 | Surface protective agent for printed matter and surface protective method for printed matter |
| CN104312267A (en) * | 2014-11-11 | 2015-01-28 | 合肥皖为电气设备工程有限责任公司 | Anti-freezing printing ink and preparation method thereof |
-
2000
- 2000-05-29 JP JP2000158854A patent/JP4050443B2/en not_active Expired - Fee Related
- 2000-09-08 CN CNB001263528A patent/CN1205281C/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1300267C (en) * | 2004-04-20 | 2007-02-14 | 东北理光株式会社 | Emulsified ink for stencil printing |
| CN101573662B (en) * | 2006-11-06 | 2012-04-18 | 东丽株式会社 | Precursor for waterless lithographic printing plate |
| CN103666100A (en) * | 2013-12-11 | 2014-03-26 | 苏州谊恒印务有限公司 | Water-based porous plate ink |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1205281C (en) | 2005-06-08 |
| JP2001164164A (en) | 2001-06-19 |
| JP4050443B2 (en) | 2008-02-20 |
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