CN100584903C - Emulsified oil ink for stencil printing - Google Patents
Emulsified oil ink for stencil printing Download PDFInfo
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- CN100584903C CN100584903C CN200610126760A CN200610126760A CN100584903C CN 100584903 C CN100584903 C CN 100584903C CN 200610126760 A CN200610126760 A CN 200610126760A CN 200610126760 A CN200610126760 A CN 200610126760A CN 100584903 C CN100584903 C CN 100584903C
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Abstract
The present invention is directed to provide a water-in-oil type emulsion ink for stencil printing, having good dispersibility, excellent water resistance and abrasion resistance, and also having high emulsion stability with time. Thus, at least one of the oil phase and the water phase of the provided emulsion ink for stencil printing comprises acetylenediol and a nonionic surfactant having a HLB value of more than 10.
Description
Technical field
The present invention relates to the emulsified ink for porous printing of the good and water-in-oil-type (w/o type) that emulsifying stability that pass in time is high of favorable dispersity, water tolerance and resistance to abrasion.
Background technology
In the typography of using hole plate print device, change the master copy data of stipulating into numerary signal, by being called as the thermoelectric converter of thermal head, based on above-mentioned signal, the version that will be called as porous body paper is bored a hole also package on printing drums.At this moment, utilize the squeezing device of printing drums bottom,, printing-ink is transferred on the printing by by the porous body paper of package.
But, be transferred to the printing ink on the printing, because it is inner and moisture evaporation is medium to air to be impregnated into printing, though dry outwardly, do not have complete drying, residual on the printing surface have undried printing ink.When the not dry printing ink after this printing during excessive the existence, its problem is that it is bad to produce unfavorable condition as described below and water tolerance or resistance to abrasion, and made dirty in the back side that stacks the printing on printing, promptly so-called " set-off (wrap up in and move り) "; Or when touching image after just having printed with hand, image is besmirched, so-called " hand touches stained (hand is wiped れ) ".Particularly, touch pollution, when existing, take place more significantly attached on hand moisture such as sweat about hand.
For solving these unfavorable conditions, propose to contain in the oil phase with respect to the water total amount be more than the 5 quality %, boiling point is 180～270 ℃ water-insoluble solvent, with respect to tinting material 1 to be the emulsified ink for porous printing (opening clear 61-255967 communique with reference to the spy) of the ratio interpolation resin 3 or more; Or use the oil-in-water-type resin emulsion as water and add the emulsified ink for porous printing (opening flat 6-220382 communique) of hydrophobic resin with reference to the spy.But its problem is, promotes the pigment cohesion, the dispersed deterioration owing to adding resin.Moreover, to pass in time and when evaporating, its problem is that viscosity possible take place to be reduced when the moisture in the printing ink, printing ink hangs from the printing ink roll gap, or because of the plastic viscosity of printing ink rises, and in press, printing ink such as leaks at unfavorable condition from the rear end of drum; The emulsifying stability of passing worsens in time.Therefore, present situation is that strong hope addresses the above problem.
Summary of the invention
The present invention finishes in view of this present situation, and problem of the present invention is, to solve above-mentioned problems in the past and to reach following purpose.That is, the objective of the invention is to, the emulsified ink for porous printing of a kind of water-in-oil-type (w/o type) is provided, this distributes ink is good, water tolerance and resistance to abrasion is good and the emulsifying stability height passed in time.
For solving above-mentioned problem, the result that the inventor furthers investigate repeatedly draws following discovery.That is, found: by oil phase and water one of at least in to contain acetylenediol and HLB value be nonionic surfactant more than 10, dispersiveness, water tolerance, resistance to abrasion and the emulsifying stability of passing in time are improved.
The present invention just is based on the invention of the inventor's above-mentioned discovery, and the method that solves above-mentioned problem is as follows.That is,
＜1〉a kind of emulsified ink for porous printing wherein, contains the oil phase of 10～50 quality % and the water of 90～50 quality %, and contain one of at least acetylenediol and the HLB value of this oil phase and water are nonionic surfactant more than 10;
＜2〉according to above-mentioned＜1〉described emulsified ink for porous printing, wherein, the HLB value is that the nonionic surfactant more than 10 is a Voranol EP 2001;
＜3〉according to above-mentioned＜2〉described emulsified ink for porous printing, wherein, Voranol EP 2001 is a polyoxyethylene oleyl ether;
＜4〉according to above-mentioned＜1 〉～＜3〉each described emulsified ink for porous printing, wherein, tinting material contains carbon black;
＜5〉according to above-mentioned＜1 〉～＜4〉each described emulsified ink for porous printing, wherein, contain the soya fatty acid Synolac in the oil phase;
＜6〉according to above-mentioned＜1 〉～＜5〉each described emulsified ink for porous printing, wherein, oil phase and water contain one of at least tinting material, acetylenediol and HLB value be the total content of the nonionic surfactant more than 10 with respect to described tinting material for surpassing 0 and be not more than 10 quality %;
＜7〉according to above-mentioned＜6〉described emulsified ink for porous printing, wherein, acetylenediol and HLB value are that the total content of the nonionic surfactant more than 10 is 1～10 quality % with respect to described tinting material;
＜8〉according to above-mentioned＜1 〉～＜7〉each described emulsified ink for porous printing, wherein, the HLB value is below 5.5;
＜9〉according to above-mentioned＜1 〉～＜8〉each described emulsified ink for porous printing, wherein, acetylenediol content is more than the 0.5 quality % with respect to tinting material;
＜10〉according to above-mentioned＜1 〉～＜9〉each described emulsified ink for porous printing, wherein, the HLB value is that the content of the nonionic surfactant more than 10 is more than the 0.5 quality % with respect to tinting material;
Emulsified ink for porous printing of the present invention contains the oil phase of 10～50 quality % and the water of 90～50 quality %, one of at least contain acetylenediol and the HLB value of this oil phase and water are nonionic surfactant more than 10, so can seek dispersiveness, water tolerance, resistance to abrasion and last the raising of emulsifying stability.
Embodiment
Emulsified ink for porous printing of the present invention contains the oil phase of 10～50 quality % and the water of 90～50 quality %, one of at least contain acetylenediol and the HLB value of this oil phase and water are nonionic surfactant more than 10, and also contain other composition as required.
Above-mentioned emulsified ink for porous printing contains the oil phase of 10～90 quality % and the water of 90～10 quality %, preferably contains oil phase 20～50 quality % and water 50～80 quality %.
When the mixture ratio less than 10 quality % of above-mentioned oil phase, can not obtain form sometimes as W/O emulsion; When surpassing 90 quality %, insufficient as the effect of W/O emulsion on physical properties sometimes.
＜water 〉
It is nonionic surfactant more than 10 that above-mentioned water contains acetylenediol and HLB value, also contains tinting material, water-soluble high-molecular compound, water, evaporation of water as required and prevents that agent or frostproofer, antiseptic-germicide, ionogen, filler pigment, O/W resin emulsion, pH from adjusting compositions such as agent.
-acetylenediol-
Acetylenediol (2,4,7,9-tetramethyl--5-decine-4,7-glycol) is to clamp the symmetrical nonionic molecule of the structure of the hydrophilic group that comprises hydroxyl and carbon-to-carbon triple bond with the hydrophobic group that branched-chain hydrocarbon forms, with following structural formula (1) expression.
Above-mentioned acetylenediol has strong hydrophilic group and hydrophobic group, thus can reduce surface tension significantly, as the moistening penetrant of water system and play a role.
Moreover, according to following reason etc., in the liquid fine bubble near the time, fit easily, thereby have defoaming effect.
1) because hydrophilic group is little, so water can not be moved into the part of the film of bubble because of the stretching, extension attenuation.
2) because be non-ionic molecule, thus between the hydrophilic group of the surfactant molecule that is had on the surfaces externally and internally of the film that steeps, do not produce electric repulsion, moreover, also, break so can not prevent the film attenuation of steeping because the steric hindrance that hydrophilic group produces is also little.
3) because on the surface of bubble with horizontal orientation, so few with the approaching part of the tensio-active agent on next door, intermolecular attraction is little.
Moreover, because be that the HLB value is 4.0 hydrophobic surfactant,, can make pigment fused mutually with nonionic surfactant so not only water tolerance but also resistance to abrasion are improved.
The content of above-mentioned acetylenediol is not particularly limited, but with respect to more than the preferred 0.5 quality % of tinting material, more preferably 0.5～50 quality %, preferred especially 0.5～1.0 quality %.
-HLB value be more than 10 nonionic surfactant-
Because above-mentioned acetylenediol is a hydrophobic surfactant,, need to add nonionic surfactant as solubilizing agent so it is dissolved in water hardly separately.
The HLB value of above-mentioned nonionic surfactant is more than 10, and is preferred 10～19, more preferably 15～19.When HLB less than 10, solubilising is insufficient; When HLB surpassed 19, the stability to emulsion impacted sometimes.
As above-mentioned HLB value is nonionic surfactant more than 10, be not particularly limited, can suitably select according to purpose, for example, can enumerate polyoxyethylene sorbitan fatty acid ester class, polyoxyethylenated castor oil-curing castor-oil plant oils, Voranol EP 2001 class, polyoxyethylene polyoxy-propylene class, polyoxyethylene alkyl phenyl ether class, Wool wax alcohols,ethoxylated-Wool wax alcohol-beeswax derivatives class etc.
As above-mentioned polyoxyethylene sorbitan fatty acid ester class, for example, can enumerate single coco-nut oil fatty acid polyoxyethylene sorbitol acid anhydride (n=20), single palmitinic acid polyoxyethylene sorbitol acid anhydride (n=20), Stearinsaeure polyoxyethylene sorbitol acid anhydride (n=20), single oleic acid polyoxyethylene sorbitol acid anhydride (n=20), single Unimac 5680 polyoxyethylene sorbitol acid anhydride (n=20) etc.
As above-mentioned polyoxyethylenated castor oil-curing castor-oil plant oils, for example can enumerate polyoxyethylene and solidify Viscotrol C (n=40,50,60) etc.
As above-mentioned Voranol EP 2001 class, for example can enumerate polyoxyethylene lauryl ether (n=21,25), polyoxyethylene oleyl ether (n=20,50) etc.
As above-mentioned polyoxyethylene polyoxy-propylene class, for example can enumerate polyoxyethylene polyoxypropylene cetyl ether (m=4/n=10, m=4/n=20, m=8/n=20), polyoxyethylene polyoxyethyl propyl decyl tetradecyl ether (m=6/n=20, m=6/n=30) etc.
As above-mentioned polyoxyethylene alkyl phenyl ether class, for example can enumerate polyoxyethylene nonylplenyl ether (n=18,20), polyoxyethylene octyl phenyl ether (n=30) etc.
As above-mentioned Wool wax alcohols,ethoxylated-Wool wax alcohol-beeswax derivatives class, for example can enumerate polyoxyethylene lanolin alcohol (n=20,40) etc.
These nonionic surfactants both can be used alone also can mix use two or more.In addition, in illustration, in the mark in bracket, n represents the polymerization degree of ethylene oxide, and m represents the polymerization degree of propylene oxide.
But, infer under the concentration of raw material nonylphenol in may reside in environment as the polyoxyethylene nonylplenyl ether that the internal secretion of Medaka is had interference effect.Therefore, preferably adopt the nonionic surfactant of the such material of environment for use hormone not, more preferably use Voranol EP 2001 classes such as polyoxyethylene lauryl ether, polyoxyethylene oleyl ether.
The content that above-mentioned HLB value is the nonionic surfactant more than 10 is not particularly limited, but is more than the 0.5 quality % with respect to tinting material preferably, more preferably 0.5～50 quality %, preferred especially 0.5～1.0 quality %.
Above-mentioned acetylenediol and HLB value are that the total content of the nonionic surfactant more than 10 is not particularly limited, but preferably with respect to tinting material for surpassing 0 and be not more than 10 quality %, more preferably 1～10 quality %, preferred especially 1～3 quality %.When above-mentioned total content surpassed 10 quality % with respect to tinting material, acetylenediol and nonionic surfactant self formed micella etc., can not get the effect of sufficient such as moistening or froth breaking effect to tinting material (pigment) sometimes.
-tinting material-
Be not particularly limited as above-mentioned tinting material, can suitably select, for example can enumerate carbon black class, metal powder, mineral dye, azo pigment, phthalocyanine pigment, fused polycycle class pigment, pigment dyestuff, oil-soluble colourant, high-visibility pigment etc. according to purpose.
As above-mentioned carbon black class, for example can enumerate acetylene black, channel black, furnace black etc.
As the carbon black of representative, for example can enumerate MA-100, MA-7, MA-70, MA-77, MA-11, #40, #44 (Mitsubishi Chemical Ind's manufacturing), Raven 1100, Raven 1080, Raven 1255, Raven 760, Raven 410 (コ ロ Application PVC ア カ one ボ Application (Colobia Carbon) corporate system) etc.
As above-mentioned metal powder, for example can enumerate aluminium powder, bronze powder etc.
As above-mentioned mineral dye, for example can enumerate red iron oxide, chrome yellow, ultramarine, chromic oxide, titanium oxide etc.
As above-mentioned azo pigment, for example can enumerate insoluble azo colour, azo lake pigment, condensed azo-pigment etc.
As above-mentioned phthalocyanine pigment, for example can enumerate metal-free phthalocyanine class pigment, copper phthalocyanine etc.
As above-mentioned fused polycycle class pigment, for example can enumerate anthraquinone class, quinoline a word used for translation ketone, isoindoline ketone, isoindoline class, dioxazine (ジ オ キ サ Application ジ Application) class, intellectual circle Lei, perylene Lei, perylene ketone (ペ リ ノ Application) class, thioindigo class, quinophthalone class, metal complex etc.
As above-mentioned pigment dyestuff, for example can enumerate the color lake of acidity or basic dyestuff etc.
As above-mentioned oil-soluble colourant, for example can enumerate diazotizing dyes, anthraquinone dyes etc.
As above-mentioned high-visibility pigment, for example be when mass polymerization synthetic resins or after the polymerization, dissolving or the painted fluorescence dye that sends various colors, the painted block body polymer resin that pulverizing obtains and carry out the material of the so-called synthetic resins sosoloid type of miniaturization, as the synthetic resins of load fluorescence dye, for example can enumerate melamine resin, urea resin, sulfonamide resin, Synolac, polyvinyl chloride (PVC) RESINS etc.
These tinting materials both can be used alone also can mix use two or more.
Preferred 0.1～10 μ m of the volume average particle size of above-mentioned tinting material, more preferably 0.1～1.0 μ m.
Preferred 2～15 quality % of the content of above-mentioned tinting material, more preferably 4～10 quality %.
In addition, tinting material also can add two or more tinting materials in water or the oil phase in the scope that can not make a very bad impression to other system.
-water-soluble high-molecular compound-
As above-mentioned water-soluble high-molecular compound, as long as can give emulsified ink for porous printing moisture retention or viscosity, just there is no particular limitation, can from known substances, suitably select as required, for example, can enumerate natural high moleculer eompound, semi-synthetic macromolecular compound, synthetic macromolecular compound etc.
As above-mentioned natural high moleculer eompound, for example, can enumerate starch, the seminose that contracts, sodium alginate, Polygalactan, tragakanta, Sudan Gum-arabic, pullulan, dextran, xanthocyte gum, gelatine, gelatin, collagen, casein etc. more.
As above-mentioned semi-synthetic macromolecular compound, for example, can enumerate carboxymethyl cellulose, methylcellulose gum, Natvosol, hydroxypropylcellulose, Vltra tears, hydroxymethyl starch, carboxymethyl starch, dialdehyde starch etc.
As above-mentioned synthetic macromolecular compound, for example, can enumerate Polyvinylpyrolidone (PVP); Acrylic resin derivatives such as polyacrylic acid, sodium polyacrylate, polyacrylic acid trolamine; Synthetic macromolecular compounds such as polyvinyl alcohol, polyacrylamide, polyoxyethylene, polyvinyl methyl ether etc.
Above-mentioned water-soluble high-molecular compound is more preferably 0.5～15 quality % below the preferred 25 quality % of the addition of above-mentioned aqueous phase.
-water-
As above-mentioned water, as long as cleaning just is not particularly limited, can suitably select according to purpose, for example can use tap water, ion exchanged water, distilled water etc.
-evaporation of water prevent agent or frostproofer-
Prevent agent or frostproofer as above-mentioned evaporation of water, be not particularly limited, can from known substances, suitably select to use, for example, can enumerate rudimentary saturated monohydroxy alcohol, glycol, polyvalent alcohol etc.They both can be used alone also can use simultaneously two or more.In addition, can use simultaneously and prevent agent and frostproofer with evaporation of water.
As above-mentioned rudimentary saturated monohydroxy alcohol, for example, can enumerate methyl alcohol, ethanol, Virahol, butanols, isopropylcarbinol etc.As above-mentioned glycol, for example, can enumerate ethylene glycol, glycol ether, propylene glycol etc.As above-mentioned polyvalent alcohol, for example, can enumerate glycerine, Sorbitol Powder etc.
Above-mentioned evaporation of water prevents agent or frostproofer below the preferred 15 quality % of the addition of above-mentioned aqueous phase, more preferably 4～12 quality %.
-antiseptic-germicide-
Above-mentioned antiseptic-germicide adds for prevent that bacterium or mould from breeding in emulsion, is effective when preserving emulsion for a long time.As this antiseptic-germicide, be not particularly limited, can from known substances, suitably select to use, for example can enumerate aromatic hydroxy compound such as Whitfield's ointment, phenols, methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate or their muriate, Sorbic Acid, dehydro-acetic acid etc.They both can be used alone also can use simultaneously two or more.
Above-mentioned antiseptic-germicide below the preferred 3 quality % of the addition of above-mentioned aqueous phase, more preferably 0.1～1.2 quality %.
-ionogen-
Above-mentioned ionogen is to add for the stability that improves emulsion, and preferred the interpolation contains improving the ionogen that the high ion of the effective lyotropic series of emulsion stability constitutes.As the high negatively charged ion of lyotropic series citrate ion, tartrate anion ion, sulfate ion, acetate ion etc. are arranged, alkalimetal ion, alkaline-earth metal ion are arranged as the high positively charged ion of lyotropic series.Here, as the ionogen that can add, preferably a negatively charged ion or a cationic side are contained above-mentioned ionic salt at least, for example, can enumerate sal epsom, sodium sulfate, Trisodium Citrate, sodium hydrogen phosphate, Sodium Tetraborate, sodium-acetate etc.Among these, preferably contain the anionic compound of divalent, special preferably sulfuric acid magnesium.These both can use a kind separately, also can use simultaneously more than 2 kinds.
Above-mentioned ionogen is at the addition of above-mentioned aqueous phase, and for example preferred 0.1～2.0 quality % is more preferably 0.5～1.5 quality %.
-filler pigment-
For preventing infiltration, adjusting viscosity, above-mentioned filler pigment can be added in oil phase, water or the two-phase.
As above-mentioned filler pigment, be not particularly limited, can suitably select according to purpose, for example can enumerate inorganic particles, organic fine particles etc.
As above-mentioned inorganic particles, for example, can enumerate from soil, silicon-dioxide, talcum, clay, lime carbonate, barium sulfate, titanium oxide, aluminium in vain, diatomite, potter's clay, mica, aluminium hydroxide etc.As above-mentioned organic fine particles, can enumerate polyacrylate resin, urethane resin, vibrin, polyvinyl resin, acrylic resin, polyvinyl chloride (PVC) RESINS, polyvinylidene chloride resin, polystyrene resin, polyorganosiloxane resin, resol, Resins, epoxy or their multipolymer etc.
There is no particular limitation for the addition of above-mentioned filler pigment in above-mentioned emulsified ink for porous printing, can suitably select according to purpose, and preferred 0.1～50 quality % is more preferably 1～5 quality %.
-oil-in-water-type (O/W) resin emulsion-
As above-mentioned oil-in-water-type (O/W) resin emulsion, have no particular limits, can from known substances, suitably select to use, both can be that synthetic macromolecular compound also can be a natural high moleculer eompound.As above-mentioned synthetic macromolecular compound, for example, can enumerate vinyl acetate resin, acrylate resin, methacrylate resin, vinyl chloride resin, ethylene-vinyl acetate copolymer, vinyl acetate-acrylic copolymer, copolymer in cinnamic acrylic ester, vinylidene chloride-acrylate copolymer, vinyl chloride-vinyl acetate copolymer, urethane resin etc.As above-mentioned natural high moleculer eompound, can enumerate and normally usedly in emulsified ink for porous printing can be added into macromolecular compound in the oil phase etc.These both can use a kind separately, also can use simultaneously more than 2 kinds.
In addition, the dispersing method for above-mentioned oil-in-water-type resin emulsion also has no particular limits, and both can add dispersion agent, protective colloid, tensio-active agent, in addition, also can be synthetic by emulsifier-free emulsion polymerization.The minimum film-forming temperature of above-mentioned oil-in-water-type resin emulsion has no particular limits, and can suitably select according to purpose, and is preferred below 40 ℃.
-pH adjustment agent-
Adjust agent as above-mentioned pH, have no particular limits, can from known substances, suitably select to use, for example, can preferably enumerate trolamine, sodium-acetate, triamylamine etc.Optionally add these pH and adjust agent, the pH that can keep water is 6～8.When the pH of water departs from above-mentioned scope, when adding water-soluble high-molecular compound, damage its effect sometimes.
＜oil phase 〉
As above-mentioned oil phase, contain emulsifying agent, oil component, antioxidant, dispersion agent, resin, gelating agent, other compositions as required and form.In addition, above-mentioned tinting material as previously mentioned.
-emulsifying agent-
As mentioned emulsifier, just have no particular limits as long as can form the emulsion of water-in-oil-type, can suitably select according to purpose, but preferred nonionic surfactant.As this nonionic surfactant, for example, can enumerate sorbitan-fatty acid ester, glycerol fatty acid ester, polyglycerol fatty acid ester, propylene glycol fatty acid ester, pentaerythritol fatty ester, polyoxyethylene sorbitan fatty acid ester, the polyoxyethylene sorbitol fatty acid ester, the polyoxyethylene glycerol fatty acid ester, cithrol, Voranol EP 2001, polyoxyethylene plant sterol ether, polyoxyethylene polyoxy-propylene, polyoxyethylene alkyl phenyl ether, polyoxyethylenated castor oil, polyoxyethylene solidifies Viscotrol C, the Wool wax alcohols,ethoxylated derivative, polyoxyethylene alkyl amine, the polyoxyethylene fatty amide, polyoxyethylene alkylphenyl formaldehyde condensation products etc., they both can use a kind separately, also can use simultaneously more than 2 kinds.
There is no particular limitation for the addition of mentioned emulsifier in above-mentioned emulsified ink for porous printing, can suitably select according to purpose, and preferred 1～8 quality % is more preferably 2.2～6.0 quality %.
The HLB value of mentioned emulsifier is preferred below 5.5, more preferably 3.0～4.7 quality %, preferred especially 3.8～4.5 quality %.
-oil component-
As above-mentioned oil component, there is no particular limitation, can suitably select according to purpose from known substances, can enumerate vegetables oil, mineral oil, synthetic wet goods.But, because above-mentioned oil component is a purpose to improve printing ink storage stability etc., therefore mixes sometimes and use the different oil of several volatility, but because ethereal oil may make a very bad impression to global environment, so preferably do not use this oil as far as possible.
As above-mentioned vegetables oil, for example, can enumerate soybean oil, Semen Maydis oil, sunflower seed oil, rapeseed oil, Thistle oil, sesame oil, Viscotrol C, synourin oil, Camellia oil, sweet oil, Oleum Cocois, Rice pollard oil, Oleum Gossypii semen, plam oil, Semen Lini oil, palm-kernel oil, tung oil, camellia caul-fat (カ メ リ ア オ イ Le), raisin seed oil, sweet almond oil, the fruit oil of Pistacia vera, Jojoba oil (ホ ホ バ oil), Macadamia ternifolia oil, メ De ウ ホ one system wet goods.They both can use a kind separately, also can use simultaneously more than 2 kinds.
As above-mentioned vegetables oil, can enumerate the material that above-mentioned vegetables oil esterification is obtained, as above-mentioned ester, for example, can enumerate methyl esters, ethyl ester, butyl ester etc.As this esterified vegetable oil, for example, preferred especially esterification soybean oil.
As above-mentioned Synolac, use the soya fatty acid Synolac of grease,, make composition total amount surpass 6% from soybean oil by using the esterification soybean oil as soybean oil, can obtain the SOY of American Soybean Association standard authentication thus, also be favourable on the security this point.
As above-mentioned mineral oil, there is no particular limitation, can suitably select according to purpose, for example, can enumerate paraffin class oil, naphthenic oil, petroleum-type solvent, spindle oil, whiteruss, light oil, kerosene, machine oil, gear oil, lubricating oil, motor lubricating wet goods, among these, preferred especially paraffin class oil, naphthenic oil, petroleum-type solvent.
As above-mentioned paraffin class oil, can use commercially available product, for example, can enumerate the ガ one go オ イ Le ア one Network テ イ Star Network series made モ one PVC Le oil company, day stone ス one パ one オ イ Le series that Shin Nihon Oil Co., Ltd makes, ダ イ ア Na プ ロ セ ス オ イ Le that Idemitsu Kosen Co., Ltd. makes, ダ イ ア Na Off レ シ ア series etc.
As above-mentioned naphthenic oil, preferably the carbon content (CN) of the cycloalkanes composition that is drawn by ring analysis is more than 30%, the carbon content of aromatic component (CA) is below 20%, and the carbon content of paraffin composition (CP) is the material below 55%, can enumerate, for example, ガ one go オ イ Le ア, the one Network テ イ Star Network オ イ Le 155 of モ one PVC Le oil company manufacturing and 300ID, ガ one go オ イ Le ア one Network テ イ Star Network オ イ Le ラ イ ト, ガ one go オ イ Le ア one Network テ イ Star Network オ イ Le C ヘ PVC one; ダ イ ア Na プ ロ セ ス オ イ Le, ダ イ ア Na Off レ シ ア series that Idemitsu Kosen Co., Ltd. makes; The サ Application セ Application オ イ Le series that Japan サ Application oil Co., Ltd. makes etc.
As above-mentioned petroleum-type solvent, can use commercially available product, for example, can enumerate ア イ ソ パ a series of (C, E, G, H, L, M etc.) and エ Network ソ one Le (D30, D40, D80, D110, D130 etc.) that エ Network ソ Application chemical company makes; AF solvent (the ソ Le ベ Application ト) series that Shin Nihon Oil Co., Ltd makes (No. 4, No. 5, No. 6, No. 7 etc.) etc.
These mineral oil, when considering ink stability etc., the preferred material that uses as the Ppolynuclear aromatic composition less than 3 quality % of the aromatic hydrocarbons that contains the above aromatic fused ring of 3 rings.Moreover, mutagen sex index (MI) less than 1.0, fragrance ingredient (%C
A) be 20～55%, aniline point is below 100 ℃, and with oily total mass is benchmark, the content of Ppolynuclear aromatics such as benzo [a] anthracene, benzo [b] fluorenes, benzo [j] fluorenes, benzo [k] fluorenes, benzo [a] pyrene, dibenzo [a, j] acridine is respectively below 10ppm, and total content is below 50ppm.
In addition, as required, aromatics oil that also can be safe to use (for example, the spy opens flat 11-80640 communique).
There is no particular limitation for the addition of above-mentioned oil component in above-mentioned emulsified ink for porous printing, can suitably select according to purpose, and preferred 3～30 quality % are more preferably 15～25 quality %.
When considering the drying property of printing ink after printing, above-mentioned oil component preferably adds and uses iodine number to be more than 100, is commonly called the oxidation inhibitor of siccative oil or semi-drying oil, but consider in the time of to make printing ink be bonded on the printing press that can use iodine number is material below 100.
Herein, the iodine number of above-mentioned oil component for example can be measured by commercially available food oils analytical equipment.As above-mentioned food oils analytical equipment, for example can enumerate oil ﹠ fat analyzer food oils analytical equipment (ヤ キ テ Network ノ ト ロ Application Co., Ltd. system) etc.
-oxidation inhibitor-
As above-mentioned oxidation inhibitor, there is no particular limitation, can from known substances, suitably select to use, for example, can enumerate nordihydroguaiaretic acid (NDGA), citrate, extraction tocopherol, tocopherol, butylhydroxy toluene, gallic acid, butylated hydroxytoluene, Tenox PG, butyl hydroxyanisole, sulfites, thiosulphate, xitix, ascorbate salt, ascorbic acid derivates etc., these both can use a kind separately, also can use simultaneously more than 2 kinds.
Below for example preferred 2 quality % of the addition of above-mentioned oxidation inhibitor in above-mentioned oil phase, more preferably 0.1～1 quality %.
Above-mentioned oxidation inhibitor, when interpolation is the antioxidant of minute quantity with respect to content of vegetable oil, the suitable antioxidant effect expected can not appear, on the contrary, when disposable interpolation with respect to content of vegetable oil is a large amount of antioxidant, play a role as oxidation promotor sometimes, moreover, also be disadvantageous aspect cost.Therefore, in order also can to suppress the oxidation of vegetables oil with a spot of antioxidant, preferably add synergist.
-synergist-
As synergist, be not particularly limited, can from known substances, suitably select, for example, can enumerate methionine(Met), xitix, Threonine, leucine, dairy protein hydrolysate, norvaline, palmitinic acid resists bad blood ester, phenylalanine, Gelucystine, tryptophane, proline(Pro), L-Ala, L-glutamic acid, Xie Ansuan, the proteinic gastric pepsin digestion liquid of pancreas, l-asparagine, arginine, malonylurea, Arsphenamine (606), ninhydrin, プ ロ パ ニ ジ Application, Histidine, nor-leucine, Phosphoric acid glycerol esters, caseic trypsin hydrolyzing liquid, caseic hydrochloric acid hydrolysis liquid etc., these both can be used alone also can use simultaneously two or more.
Preferred 0.1～1 quality % of the addition of above-mentioned synergist.
-dispersion agent-
Above-mentioned dispersion agent appends when preferably also adding tinting material in oil phase.
As above-mentioned dispersion agent, there is no particular limitation, can suitably select according to purpose, for example, can enumerate the alkyl amine macromolecular compound, the aluminum chelate compounds, phenylethylene-maleic anhydride class copolymerized macromolecule compound, polycarboxylate type macromolecular compound, the aliphatic category polycarboxylic acid, the amine salt class of macromolecule polyester, ester type anion surfactant, the long-chain amine salt of high molecular poly carboxylic acid, the salt of long-chain polyaminoamide and polymer acid polyester, polyamide-based compound, the phosphoric acid ester tensio-active agent, the alkylthio metal carboxylate, the sulfonated class, dioctyl sulfo-succinic acid salt, polymine, the alcohol amine salt, the resin with insoluble tinting material divergent function of Synolac etc. etc.In addition, as long as in the scope of the storage stability that does not damage printing ink, also can enumerate ionic species tensio-active agent, hydrophilic and oleophilic surfacant etc.These dispersion agents both can add a kind separately, also can mix to add or more than 2 kinds.
Below the 40 quality % of the preferred tinting material of addition of the dispersion agent except that above-mentioned polymer and resin, more preferably 2～35 quality %.
Above-mentioned Synolac, when adding the high-molecular weight resin, dispersion stabilization to insoluble tinting material is effective especially, but Synolac is when using separately or using simultaneously with other dispersion agent, and the addition of resin is with respect to more than the preferred 0.05 quality % of tinting material.
-resin-
As above-mentioned resin, there is no particular limitation, can suitably select according to purpose from known substances, for example, can enumerate Synolac, rosin; Rosin based resins such as polymerized rosin, staybelite, rosin ester, rosen polyester resin, hydrogenated wood rosin glycerol ester; Modified rosin resins such as rosin modified alkyd resin, Abietyl modified maleic acid resin, rosin modified phenolic resin; Maleic acid resin; Resol; Petroleum resin; Rubber derivative resins such as thermoprene; Terpine resin; Polymerized castor oils etc., they both can use a kind separately, also can use simultaneously more than 2 kinds.Among these, special preferred alcohols acid resin.
The weight-average molecular weight of above-mentioned resin is from the viewpoint of fixation performance and printing adaptability, and is preferred 8000～160,000, is more preferably 30,000～80,000.
The addition of above-mentioned resin in above-mentioned oil phase, from the viewpoint of the cost and the printing adaptability of printing ink, preferred 2～50 quality % are more preferably 5～20 quality %.
When the weight-average molecular weight of above-mentioned resin is low and addition after a little while, little to the effect of fixation performance, on the other hand, weight-average molecular weight is too high, or resin content is for a long time, the viscosity of printing ink uprises, and produces printing ink from printing adaptability problems such as the drum rear end spill.
As above-mentioned resin, can use commercially available product, can enumerate KG-836, KG-846, KG-1801, KG-1832, KG-1829, KG-1804, KG-1828, KG-1808-1, KG-1834, KG-1831, KG-1833, タ マ ノ Le 353, タ マ ノ Le 403, タ マ ノ Le 371, タ マ ノ Le 394 that Arakawa Chemical Industries, Ltd. makes; Ha リ マ changes into Ha リ Off エ ノ one Le that Co., Ltd. makes (561,564,582,173, T3120, T3040, P637,295) etc.In addition, thermoprene also produces effect to fixation performance, for example, can enumerate trade(brand)name ALSYNOL RS47, ALSYNOL RS44, SYNTEX 800 that コ ロ Application PVC ヤ Application カ one ボ Application Japanese firm makes; ALPEX CK 450, ALPEX CK514 etc. that ヘ キ ス ト company makes.
Above-mentioned Synolac contains grease and polyprotonic acid and polyvalent alcohol usually.As above-mentioned grease, can enumerate, for example, and Oleum Cocois, plam oil, sweet oil, Viscotrol C, Rice pollard oil, continuous seed oil, soybean oil, Semen Lini oil, tung oil etc., among these, preferred especially soybean oil.As above-mentioned polyprotonic acid, can use in saturated polybasic acid and the unsaturated polyprotonic acid any one.As above-mentioned saturated polybasic acid, can enumerate, for example, Tetra hydro Phthalic anhydride, m-phthalic acid, terephthalic acid, succsinic acid, hexanodioic acid, sebacic acid, tetrahydrophthalic acid etc.As above-mentioned unsaturated polyprotonic acid, can enumerate, for example, toxilic acid, maleic anhydride, fumaric acid, methylene-succinic acid, citraconic anhydride etc.
As above-mentioned polyvalent alcohol, for example, can enumerate ethylene glycol, glycol ether, triglycol, polyoxyethylene glycol, propylene glycol, 1, ammediol, 1,4-butyleneglycol, glycerine, TriMethylolPropane(TMP), neopentyl glycol, Glycerol dimer, two triglycerols, tetramethylolmethane, dipentaerythritol, mannitol, Sorbitol Powder etc.
Above-mentioned Synolac, preferred acid number are below 15, to be more preferably below 10.In addition, iodine number preferably more than 80, is more preferably 80～110.In addition, the quality % in the resin the when oil length of above-mentioned Synolac exists with the state of tri-glyceride with the lipid acid in the above-mentioned grease represents, usually preferred 60～90 quality %.The weight-average molecular weight of above-mentioned Synolac is preferred below 30,000, is more preferably below 10,000.
Here, the acid number of above-mentioned Synolac can be measured by for example JIS K0070.The iodine number of above-mentioned Synolac can be measured by for example JIS K0070.
-gelating agent-
Above-mentioned gelating agent has the resin gelization that contains in the oil phase, improves the effects such as storage stability, fixation performance and flowability of printing ink, preferably with oil phase in the compound of resin complex bonding.As this gelating agent, can enumerate, for example, contain the organic acid salt of metals such as Li, Na, K, Al, Ca, Co, Fe, Mn, Mg, Pb, Zn, Zr, organic chelated compound, metallic soap oligopolymer etc.Particularly, can enumerate organic chelated compounds such as stearate such as metallic naphthenate, Zinic stearas such as sad metal-salt such as aluminium octoate, manganese naphthenate, single acetyl ethyl acetate aluminum-diisopropoxide etc.These both can use a kind separately, also can use simultaneously more than 2 kinds.
The addition of above-mentioned gelating agent, there is no particular limitation, can suitably select according to purpose, and preferably the total amount with respect to the resin in the oil phase is below the 15 quality %, is more preferably 5～10 quality %.
In addition, in emulsified ink for porous printing of the present invention,, separates well with printing drums, or the volume that prevents printing wrinkles (rolling up Ga り on the I) etc., can in oil phase, add wax for making printing in when printing.In addition, by adding trolamine or sodium hydroxide etc. to aqueous phase, and add water-soluble high-molecular compound, can further promote high viscosityization.Have again, add rust-preventive agent or defoamer, can when printing, prevent printing press owing to printing ink gets rusty, or printing ink bubble to aqueous phase.The known product that these additives can optionally add in the emulsified ink for porous printing to be added, the amount of its interpolation can be roughly the same with the situation of product in the past.
The HLB value of-emulsified ink for porous printing-
The HLB value of above-mentioned emulsified ink for porous printing, be not particularly limited, but consider from the stable viewpoint separating of oil or that seek at high temperature that improves emulsifying stability, suppress to pass in time, preferred below 5.5, more preferably 3.0～5.5, further preferred 3.0～4.7, most preferably 3.8～4.5.When above-mentioned HLB value surpassed 5.5, because the easy generation of passing in time is separating of oil, the stability when high temperature reduced sometimes; When less than 3.0, be difficult to emulsification sometimes.
Here, the HLB value of above-mentioned emulsified ink for porous printing is to be added into the acetylenediol of water and the HLB value is nonionic surfactant more than 10 and the weighted mean that is added into each emulsifying agent of oil phase.
Particularly, be to be nonionic surfactant and each emulsifying agent HLB value separately more than 10 with above-mentioned acetylenediol, HLB value, multiply by the value that the content (quality %) of above-mentioned each composition in emulsified ink for porous printing obtains, again (quality %) and value that obtain divided by the content of above-mentioned each composition in emulsified ink for porous printing.
For example, be the acetylenediol of 0.04 quality %, be that the HLB value of 0.04 quality % is 13.5 nonionic surfactant, is the HLB value of 5.8 quality % when being 4.3 emulsifying agent with respect to emulsified ink for porous printing that the HLB value of above-mentioned emulsified ink for porous printing can be tried to achieve by following calculating formula and is " 4.36 " when containing with respect to emulsified ink for porous printing with respect to emulsified ink for porous printing.
Calculating formula:
(4.0×0.04+13.5×0.04+4.3×5.8)÷(0.04+0.04+5.8)
Moreover, be the acetylenediol of 0.04 quality %, be that the HLB value of 0.04 quality % is 18.0 nonionic surfactant, is that the HLB value of 0.5 quality % is 4.0 emulsifying agent, is the HLB value of 5.8 quality % when being 4.3 emulsifying agent with respect to emulsified ink for porous printing that the HLB value of above-mentioned emulsified ink for porous printing can be tried to achieve by following calculating formula and is " 4.36 " with respect to emulsified ink for porous printing when containing with respect to emulsified ink for porous printing with respect to emulsified ink for porous printing.
Calculating formula:
(4.0×0.04+18×0.04+4.0×0.5+4.3×5.8)÷(0.04+0.04+0.5+5.8)
-manufacture method-
Manufacture method as emulsified ink for porous printing of the present invention, there is no particular limitation, can from known method, suitably select according to purpose, for example, can be by preparing oil phase and water liquid respectively in advance with ordinary method, water is added in the above-mentioned oil phase, in known mulsers such as dispersion mixer, high-speed uniformly mixing device, high-pressure homogenizer, carry out emulsification and make.
Particularly, blending emulsifiers, oil component etc. stir by high speed dissolver.Afterwards, carry out dispersion treatment, the preparation oil phase with sand mill.On the other hand, mix acetylenediol, HLB value and be nonionic surfactant more than 10, water-soluble polymer, frostproofer, antiseptic-germicide, ionogen etc., this mixed solution is dissolved in water well, prepare water.Then, use mulser, the above-mentioned oil phase liquid of packing into, the limit stirred liq, the limit is added above-mentioned water liquid slowly and is carried out emulsification, thus, can produce emulsified ink for porous printing.
Emulsified ink for porous printing of the present invention is 20sec in velocity of shear
-1The time the preferred 3～40Pas of viscosity, be more preferably 10～30Pas.
-purposes-
As described above, therefore emulsified ink for porous printing favorable dispersity of the present invention, water tolerance and resistance to abrasion is good and the emulsifying stability height passed in time go for for example adopting wheel to change the porous printing that porous printer carries out.
By the present invention, a kind of water-in-oil-type (w/o type) emulsified ink for porous printing can be provided, this printing ink can solve in the past the problems that exist, and can provide favorable dispersity, water tolerance and resistance to abrasion good and emulsifying stability that pass in time is high.
Embodiment
Below, embodiments of the invention are described, but the present invention is not subjected to any qualification of these embodiment.
(embodiment 1)
The preparation of-emulsified ink for porous printing-
At first, prescription blending emulsifiers and oil component according to table 1 record stir by high speed dissolver.Afterwards, carry out dispersion treatment, the preparation oil phase with sand mill (LMZ2, ア シ ザ ワ Off ア イ Application テ Star Network Co., Ltd. system).
Then, prescription according to table 1～3 records, with the pre-dispersed tinting material of dispersion mixer (special machine corporate system, T.K.HOMOMIXER), acetylenediol, nonionic surfactant, water-soluble polymer, water, frostproofer, antiseptic-germicide and ionogen, then, formally disperse the preparation water with sand mill (LMZ0.6, ア シ ザ ワ Off ア イ Application テ Star Network Co., Ltd. system).
Then, use mulser (daylight ケ ミ カ Le ズ Co., Ltd. system, emulsion test machine ET-3A type), the above-mentioned oil phase liquid of packing into, the limit stirred liq, above-mentioned water liquid is added on the limit slowly, by above method, makes the emulsified ink for porous printing of embodiment 1.
(embodiment 2～11 and comparative example 1～4)
In embodiment 1, except that changing to the composition shown in table 1～3, other makes each routine emulsified ink for porous printing similarly to Example 1.
[evaluation]
Then, each emulsified ink for porous printing about obtaining carries out following evaluation.
(1) mensuration of jitter time
Use sand mill (LMZ0.6, ア シ ザ ワ Off ア イ Application テ Star Network Co., Ltd. system), measuring that volume average particle size up to tinting material becomes is the time of 10 μ m.In addition, above-mentioned volume average particle size is measured by LA-700 (the hole field makes made).
(2) evaluation of water tolerance and resistance to abrasion
The Satelio A400 printed images made from northeast リ コ one company, moistening cloth wiping divides following Three Estate, with visual valuation stained (wiping れ) level at this moment through the above-mentioned image after 30 minutes with immersion.
Zero: almost do not find the stained of image
△: find that image has stained slightly.
*: find the stained remarkable of image.
(3) evaluation of Pao generation level.
Divide following Three Estate, with the pre-dispersed moderate foaming generation level of visual valuation by dispersion mixer (special machine corporate system, T.K.HOMOMIXER).
Zero: almost do not find the generation of bubble.
△: find to produce a spot of bubble.
*: the generation of finding bubble is obvious.
(4) mensuration of centrifugal separating of oil amount
By separating centrifuge (Co., Ltd.'s assistant is made made, M150-IVD for a long time), under 6300G, after making, centrifugation in 3 hours places the printing ink in 2 weeks down, then at 60 ℃, with consequent oil content with respect to the ratio of ink quality as centrifugal separating of oil amount, calculate by percentage.
(5) evaluation of high-temperature stability
Under 60 ℃, the printing ink of making was placed 45 days, divide following Three Estate, the state of the printing ink after placing with visual valuation.
Zero: outward appearance is no problem fully.
△: You Heshui separates a little.
*: oil and water sepn.
The result of above-mentioned (1)～(5) is shown in table 1～3.In addition, the unit of each composition in table 1～3 is " quality % ".
Table 1
Table 2
Table 3
In table 1～3, polyglyceric acid fatty acid esters is used the poly-ricinoleate of six glycerine of daylight ケ ミ カ Le ズ corporate system, sorbitanic alcohol acid anhydride monoleate uses the SO-10 of daylight ケ ミ カ Le ズ corporate system, naphthenic oil uses the system SUNTHEN380 of Japanese サ Application oil company, methyl soyate uses the Vertecbio Gold #4 of Vertec Biosolvents corporate system, carbon black 1 uses the Raven1080 of コ ロ Application PVC ア カ one ボ Application corporate system, carbon black 2 uses the Raven760 of コ ロ Application PVC ア カ one ボ Application corporate system, acetylenediol uses サ one Off イ ノ one Le 104 of エ ア プ ロ ダ Network Star corporate system, nonionic surfactant uses the Voranol EP 2001 class or the polyoxyethylene alkyl phenyl ether class of daylight ケ ミ カ Le ズ corporate system, water-soluble polymer uses the Luvitec K30 solution of BASF AG's system, antiseptic-germicide uses the デ Le ト Star プ 512 of Japanese エ Application バ イ ロ ケ ミ カ Le ズ corporate system, frostproofer uses the glycerine of Nof Corp.'s system, ionogen uses sal epsom 7 hydrates of Northeast chemical company system.
Moreover, in table 1～3, HLB value (calculated value) is with acetylenediol, nonionic surfactant and each emulsifying agent HLB separately value that obtains with the content (quality %) of above-mentioned each composition in emulsified ink for porous printing on duty, again (quality %) and the value that obtain divided by the content of above-mentioned each composition in emulsified ink for porous printing.
Result according to table 1～3, can judge: contain the emulsified ink for porous printing that acetylenediol and HLB value are the embodiment 1～11 of the nonionic surfactant more than 10, the good and emulsifying stability height that pass in time of favorable dispersity, water tolerance and resistance to abrasion.Particularly, can also judge: acetylenediol and HLB value are that the total content of the nonionic surfactant more than 10 is below the 10 quality % with respect to above-mentioned tinting material, the HLB value is below 5.5 and acetylenediol and HLB value are that the content of the nonionic surfactant more than 10 is embodiment 1～4 more than the 0.5 quality % and 11 emulsified ink for porous printing with respect to tinting material, jitter time is short, almost do not find the generation of the stained of image or bubble, therefore centrifugal separating of oil amount can seek further to improve dispersiveness also less and the high-temperature stability height, water tolerance, resistance to abrasion and the emulsifying stability of passing in time.In addition, because in the emulsified ink for porous printing of embodiment 8, acetylenediol and HLB value are that the total content of the nonionic surfactant more than 10 reaches 15 quality % with respect to tinting material; Because in the emulsified ink for porous printing of embodiment 10, the HLB value of this emulsified ink for porous printing is up to 5.62, so obtain all many results of centrifugal separating of oil amount of these two embodiment in addition.
Emulsified ink for porous printing of the present invention, therefore good the and emulsifying stability height that pass in time of favorable dispersity, water tolerance and resistance to abrasion goes for for example changeing the porous printing that porous printer carries out with wheel.
Claims (10)
1. an emulsified ink for porous printing wherein, contains the oil phase of 10～50 quality % and the water of 90～50 quality %, and contain one of at least acetylenediol and the HLB value of this oil phase and water are nonionic surfactant more than 10.
2. according to the described emulsified ink for porous printing of claim 1, wherein, the HLB value is that the nonionic surfactant more than 10 is a Voranol EP 2001.
3. according to the described emulsified ink for porous printing of claim 2, wherein, Voranol EP 2001 is a polyoxyethylene oleyl ether.
4. according to the described emulsified ink for porous printing of claim 1, wherein, wherein, oil phase and water one of at least contain tinting material, described tinting material contains carbon black.
5. according to the described emulsified ink for porous printing of claim 1, wherein, contain the soya fatty acid Synolac in the oil phase.
6. according to the described emulsified ink for porous printing of claim 1, wherein, oil phase and water contain one of at least tinting material, acetylenediol and HLB value be the total content of the nonionic surfactant more than 10 with respect to described tinting material for surpassing 0 and be not more than 10 quality %.
7. according to the described emulsified ink for porous printing of claim 6, wherein, acetylenediol and HLB value are that the total content of the nonionic surfactant more than 10 is 1～10 quality % with respect to described tinting material.
8. according to the described emulsified ink for porous printing of claim 1, wherein, the HLB value of this emulsified ink for porous printing is below 5.5.
9. according to the described emulsified ink for porous printing of claim 6, wherein, acetylenediol content is more than the 0.5 quality % with respect to tinting material.
10. according to the described emulsified ink for porous printing of claim 6, wherein, the HLB value is that the content of the nonionic surfactant more than 10 is more than the 0.5 quality % with respect to tinting material.
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| JP2005257411A JP4845457B2 (en) | 2005-09-06 | 2005-09-06 | Emulsion ink for stencil printing |
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| JP5315780B2 (en) * | 2008-05-12 | 2013-10-16 | 株式会社リコー | Emulsion ink for stencil printing |
| US20100063186A1 (en) * | 2008-09-11 | 2010-03-11 | Sanford, L.P. | Washable ink compositions and writing instruments comprising same |
| WO2012055107A1 (en) * | 2010-10-28 | 2012-05-03 | 深圳智慧天使投资有限公司 | Water-in-oil emulsion ink composition and use thereof |
| CN104356758B (en) * | 2014-10-08 | 2017-10-27 | 王宝林 | Oil ink in a kind of oil-in-water type emulsion of safety non-toxic |
| CN114829512B (en) * | 2019-12-20 | 2023-08-11 | 哈利玛化成株式会社 | Resin composition for aqueous ink |
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| JPH06220383A (en) * | 1993-01-27 | 1994-08-09 | Dainippon Printing Co Ltd | Ink for stencil printing |
| JP2000345088A (en) * | 1999-06-03 | 2000-12-12 | Riso Kagaku Corp | Stenciling emulsion ink |
| JP4240188B2 (en) * | 2001-03-21 | 2009-03-18 | 日信化学工業株式会社 | Water-soluble surfactant composition |
| JP2003292852A (en) * | 2002-04-05 | 2003-10-15 | Sharp Corp | Recording liquid composition |
| JP4510404B2 (en) * | 2003-05-20 | 2010-07-21 | 東北リコー株式会社 | W / O emulsion ink for stencil printing |
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