CN100355842C - Emulsified oil ink for stencil printing - Google Patents
Emulsified oil ink for stencil printing Download PDFInfo
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- CN100355842C CN100355842C CNB2005100990483A CN200510099048A CN100355842C CN 100355842 C CN100355842 C CN 100355842C CN B2005100990483 A CNB2005100990483 A CN B2005100990483A CN 200510099048 A CN200510099048 A CN 200510099048A CN 100355842 C CN100355842 C CN 100355842C
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Abstract
Emulsion ink has oil phase (10-90 mass%) containing dispersant and aqueous phase (90-10 mass%) containing water insoluble coloring agent.
Description
Technical field
The present invention relates to water-in-oil-type (w/o type) emulsified ink for porous printing of airborne shelf-stability excellence.
Background technology
As everyone knows, stencil printing method is to use the porous printing body paper (hole version) with punching portion, and the punching portion by this hole version is by a side direction opposite side moving ink of hole version, is printed at paper etc. on the face of thing to carry out method of printing.In this stencil printing method, can use water-in-oil-type (w/o type) emulsified ink that contains volatile solvent, nonvolatile solvent, resin, tinting material, tensio-active agent, water, frostproofer, ionogen and sanitas usually.
As such emulsified ink for porous printing, for example proposed, in oil phase, contain tinting material and resin, by the effect of this resin, seek to improve emulsified ink for porous printing (opening flat 11-310740 communique) with reference to the spy to the anchorage of paper.The printing ink that contains colorant type in oil phase in this scheme because tinting material is scattered in the oil component of non-volatility, therefore, is placed on printing press for a long time, and after the volatile component evaporation, printing ink can not solidify yet.But in this scheme, tinting material also infiltrates into paper inside at oil in the paper infiltration, therefore, exists the image color with respect to colorant concentration to reduce, and in addition, is easy to generate the problem that image is spread and sunk in and oozed.
In addition, the spy opens and has proposed aqueous phase in the flat 9-31384 communique and contain tinting material and resin, seeks to improve the emulsified ink for porous printing to the anchorage of paper.In this scheme, tinting material is scattered in the printing ink of aqueous phase type, because tinting material do not permeate with oil, so tinting material is stranded in paper surface, so the image color height, spread and sink in and ooze less.But, in this scheme, exist image to the friction patience a little less than shortcoming.Therefore, add resin at aqueous phase, but added in the system of tinting material at aqueous phase because tinting material is scattered in volatile water, have moisture evaporation after, tinting material is dry solidification on printing press, stops up the problem of mesh.
Therefore, present present situation is, also do not obtain can not producing with the water-insoluble tinting material be added in the printing ink that aqueous phase obtains since the mesh that the set of the water-insoluble tinting material after long-time the placement causes stop up, and the emulsified ink for porous printing of the water-in-oil-type of airborne shelf-stability excellence (w/o type), therefore wishing provides as early as possible.
Summary of the invention
The objective of the invention is to, provide a kind of improvement to add the water-insoluble tinting material to printing ink that aqueous phase obtains and place the back because the mesh that the set of this water-insoluble tinting material causes stops up, and the emulsified ink for porous printing of the water-in-oil-type of airborne shelf-stability excellence (w/o type).
For solving above-mentioned problem, the result that the present inventor furthers investigate repeatedly draws following discovery.Promptly, found, contain oil phase 10～90 quality % and water 90～10 quality % if adopt, contain the water-insoluble tinting material with this aqueous phase, and the emulsified ink for porous printing that in above-mentioned oil phase, contains dispersion agent, just can improve the water-insoluble tinting material add to after long-time placement of printing ink that aqueous phase obtains because the generation that the mesh that the set of this water-insoluble tinting material causes stops up.
＜1〉a kind of emulsified ink for porous printing is characterized in that, contains oil phase 10～90 quality % and water 90～10 quality %, and this aqueous phase contains the water-insoluble tinting material, and contains dispersion agent in above-mentioned oil phase.
In above-mentioned＜1〉record emulsified ink for porous printing in, owing in above-mentioned oil phase, add dispersion agent, cause in the coloring components agglutinative process in the water volatilization, dispersion agent in the oil phase acts on the tinting material that contains moisture, can prevent that agglutinative is scattered in tinting material in the oil phase simultaneously between the tinting material.
＜2〉according to above-mentioned＜1〉record emulsified ink for porous printing, wherein, aqueous phase also contains dispersion agent.
＜3〉according to above-mentioned＜1〉emulsified ink for porous printing put down in writing, wherein, the dispersion agent in the oil phase is the polyesteramine compounds.
＜4〉according to above-mentioned＜1〉emulsified ink for porous printing put down in writing, wherein, the dispersion agent in the oil phase is an ammonium substituted phthalocyanine sulfonic acid class dispersion agent.
Use above-mentioned＜3〉and＜4 in during the dispersion agent of any record, significantly improve and place the back for a long time because the mesh that the set of water-insoluble tinting material causes stops up.
＜5〉according to above-mentioned＜1〉emulsified ink for porous printing put down in writing, wherein, the water-insoluble tinting material is a pigment.
＜6〉according to above-mentioned＜5〉emulsified ink for porous printing put down in writing, wherein, pigment is any one in carbon black and the phthalocyanine pigment.
＜7〉according to above-mentioned＜1〉emulsified ink for porous printing put down in writing, wherein, the addition of dispersion agent is 40 mass parts or below 40 mass parts with respect to water-insoluble tinting material 100 mass parts.
＜8〉according to above-mentioned＜1〉emulsified ink for porous printing put down in writing, wherein, it is water-miscible organic solvent more than 220 ℃ or 220 ℃ that aqueous phase contains boiling point.
＜9〉according to above-mentioned＜8〉emulsified ink for porous printing put down in writing, wherein, boiling point is that the water-miscible organic solvent more than 220 ℃ or 220 ℃ is a glycerine.
In above-mentioned＜8〉and＜9 in any emulsified ink for porous printing of being put down in writing in, by at aqueous phase interpolation boiling point being the water-miscible organic solvent more than 220 ℃ or 220 ℃, can prevent the dry set of tinting material on printing press, and then obtain the emulsified ink of airborne shelf-stability excellence.
＜10〉according to above-mentioned＜1〉emulsified ink for porous printing put down in writing, wherein, contain the soya fatty acid Synolac in the oil phase.
The preferred plan that carries out an invention
Emulsified ink for porous printing of the present invention contains oil phase 10～90 quality % and water 90～10 quality %, and this aqueous phase contains the water-insoluble tinting material, contains dispersion agent in the above-mentioned oil phase, optionally, can also contain other compositions.
By in above-mentioned oil phase, containing dispersion agent.Can bring into play following effect: cause that in the water volatilization dispersion agent in the oil phase acts on the tinting material that contains moisture in the tinting material agglutinative process, can prevent that agglutinative is scattered in tinting material in the oil phase simultaneously between the tinting material.
Above-mentioned emulsified ink for porous printing contains oil phase 10～90 quality % and water 90～10 quality %, preferably contains oil phase 20～50 quality % and water 80～50 quality %.
During the blending ratio less than 10 quality % of above-mentioned oil phase, can not be made as the form of W/O emulsion, and when surpassing 90 quality %, on rerum natura, disappear as the effect of W/O emulsion.
-dispersion agent-
As above-mentioned dispersion agent, can use and be dissolved respectively by oil phase and water and have the surfactivity energy, and do not hinder the material that emulsion forms, can use emulsifying agent described later (nonionic surfactant) and water-soluble high-molecular compound yet as dispersion agent.
As above-mentioned dispersion agent, there is no particular limitation, can suitably select according to purpose, can enumerate, for example, two (2-ethylhexyl) sodium sulfosuccinate (OTP-75, daylight ケ ミ カ Le ズ Co., Ltd. system), the alkyl amine macromolecular compound, the aluminum chelate compounds, phenylethylene-maleic anhydride class copolymerized macromolecule compound, the polyglycerol fatty acid ester compounds, the polyesteramine compounds, 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 polymkeric substance of N-alkyl-substituted acrylamide classes such as PNIPAM or its multipolymer, sulfonated class, dioctyl sulfo-succinic acid salt, polymine, pure amine salt, acetylenediol compounds, polyethylene oxide nonylplenyl ether, polyethylene oxide alkylamine, polyethylene oxide alkyl ethers etc.In addition, as long as in the scope of the storage stability that does not damage printing ink, also can use ionic surfactant, amphoterics etc., they can a kind use separately, also can use simultaneously more than 2 kinds or 2 kinds.Among these, special preferred polyester aminated compounds.
Above-mentioned polyesteramine compounds is to have the polyester of free carboxy acid's base and the resultant of reaction of poly-(low alkylidene group) imines, is to have two polyester chains at least and gather (low alkylidene group) imines chain to be combined in the compound on this polyester chain respectively.
As above-mentioned polyesteramine compounds, can enumerate, for example, UK Patent Application discloses the system ソ of Lubrizol society Le ス パ one ズ that puts down in writing in No. 2001083 specification sheets etc.
In addition, when the pigment that makes an addition to water is phthalocyanine pigment or carbon black, is more preferably and uses the phthalocyanine sulfonic acid class dispersion agent (for example, ソ Le ス パ one ズ 5000) that replaces with ammonium simultaneously.
As dispersion agent, can use commercially available product, can enumerate, for example, プ レ Application ア Network ト AL-M, ア ジ ス パ one PN411 (being monosodium glutamate Off ア イ Application テ Network ノ society system); 5000,13940,16000,17000,20000,28000,54000 (Lubrizol society systems) of ソ Le ス パ one ズ series; OTP-75, NP-15 (being daylight ケ ミ カ Le ズ Co., Ltd. system) etc.They can a kind use separately, also can use simultaneously more than 2 kinds or 2 kinds.
The addition of above-mentioned dispersion agent has no particular limits, can suitably select according to purpose, be 100 mass parts or below 100 mass parts preferably, be more preferably 40 mass parts or below 40 mass parts, preferred especially 0.1～35 mass parts for tinting material 100 mass parts of aqueous phase.When above-mentioned addition surpasses 100 mass parts, bring influence can for the emulsifying stability of printing ink, in addition, cost raises.
＜oil phase 〉
As above-mentioned oil phase, there is no particular limitation, can suitably select according to purpose, contains oil component, emulsifying agent, resin, gelating agent, oxidation inhibitor and filler pigment, optionally, can also contain other compositions and form.
-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 wet goods.
As above-mentioned vegetables oil, can enumerate, for example, the fruit oil of soybean oil, Semen Maydis oil, sunflower seed oil, rape seed 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 oil, raisin seed oil, sweet almond oil, Pistacia vera, Jojoba oil (ホ ホ バ oil), Macadamia ternifolia oil, メ De ウ ホ one system wet goods.They can a kind use separately, also can use simultaneously more than 2 kinds or 2 kinds.
As above-mentioned esterified vegetable oil, can enumerate, with the material that above-mentioned vegetables oil esterification obtains,, can enumerate as above-mentioned ester, for example, methyl esters, ethyl ester, butyl ester etc.As this esterified vegetable oil, can enumerate, for example, esterification soybean oil, esterification Yatall MA.
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, obtaining the SOY of American Soybean Association standard authentication, also is favourable on the security this point.
Preferred 1～35 quality % of the addition of above-mentioned vegetables oil in emulsified ink for porous printing is more preferably 5～25 quality %.
As above-mentioned mineral oil, there is no particular limitation, can suitably select according to purpose, for example, 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, can enumerate, for example, the ダ イ ア Na プ ロ セ ス オ イ Le of the day stone ス one パ one オ イ Le series of the ガ one go オ イ Le ア one Network テ イ Star Network series of モ one PVC Le oil society manufacturing, Shin Nihon Oil Co., Ltd's manufacturing, Idemitsu Kosen Co., Ltd.'s manufacturing, 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% or 30%, the carbon content of aromatic component (CA) is below 20% or 20%, and the carbon content of paraffin composition (CP) is the material below 55% or 55%, can enumerate, for example, side's one go オ イ Le ア, one Network テ イ Star Network オ イ Le 155 of モ one PVC Le oil society manufacturing and 300ID, ガ one go オ イ Le ア one Network テ イ Star Network 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 ア 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, can enumerate, for example, 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 chemistry society makes; AF solvent (the ソ Le ベ Application ト) series (No. 4, No. 5, No. 6, No. 7) that Shin Nihon Oil Co., Ltd makes 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 or 3 rings.In addition, mutagen sex index (MI) less than 1.0, fragrance ingredient (%C
A) be 20～55%, aniline point is below 100 ℃ or 100 ℃, and with oily total mass is benchmark, benzo [a] anthracene, benzo [b] fluorenes, benzo [j] fluorenes, benzo [k] fluorenes, benzo [a] pyrene, dibenzo [a, j] content of Ppolynuclear aromatic such as acridine is respectively at 10ppm or below the 10ppm, and total content is at 50ppm or below the 50ppm.
In addition, optionally, 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 mineral oil in above-mentioned emulsified ink for porous printing, can suitably select according to purpose, and preferred 1～35 quality % is more preferably 5～25 quality %.
-emulsifying agent-
As emulsifying agent, get final product so long as can form the emulsion of water-in-oil-type, have no particular limits, can suitably select according to purpose, but preferred especially nonionic class tensio-active agent.As this nonionic class tensio-active agent, can enumerate, for example, sorbitan-fatty acid ester, glycerol fatty acid ester, polyglycerol fatty acid ester, propylene glycol fatty acid ester, pentaerythritol fatty ester, the polyethylene oxide sorbitan-fatty acid ester, polyethylene oxide Sorbitol Powder fatty acid ester, the polyethylene oxide glycerol fatty acid ester, cithrol, polyethylene oxide alkyl ethers, polyethylene oxide plant sterol ether, polyethylene oxide poly(propylene oxide) alkyl oxide, the polyethylene oxide alkyl phenyl ether, the polyethylene oxide Viscotrol C, the polyethylene oxide hardened castor oil, polyethylene oxide hydrous wool derivative, the polyethylene oxide alkylamine, the polyethylene oxide fatty amide, polyethylene oxide alkyl phenyl formaldehyde condensation products etc., they can a kind use separately, also can use simultaneously more than 2 kinds or 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 0.5～15 quality % is more preferably 2～8 quality %.
-resin-
As above-mentioned resin, there is no particular limitation, can suitably select according to purpose from known substances, can enumerate, for example, 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 can a kind use separately, also can use simultaneously more than 2 kinds or 2 kinds.Among these, special preferred alcohols acid resin.
The weight-average molecular weight of above-mentioned resin (Mw) is from the viewpoint of fixation performance and printing adaptability, and is preferred 8,000～160,000, 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 such as spills at printing adaptability from the drum rear end problem.
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, マ ノ Le 353, マ ノ Le 403, マ ノ Le 371, 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, can enumerate, for example, trade(brand)name ALSYNOL RS47, ALSYNOL RS44, SYNTEX 800 that コ ロ Application PVC ヤ Application カ one art Application Japan society makes; ALPEX CK 450, ALPEX CK514 etc. that ヘ キ ス ト society 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 any one of saturated polybasic acid and unsaturated polyprotonic acid.As above-mentioned saturated polybasic acid, can enumerate, for example, Tetra hydro Phthalic anhydride, m-phthalic acid, terephthalic acid, succsinic acid, adipic 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, can enumerate, for example, 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 or 15, are more preferably below 10 or 10.In addition, the iodine number of above-mentioned Synolac preferably more than 80 or 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 %.Below the weight-average molecular weight of above-mentioned Synolac preferred 30,000 or 30,000, be more preferably below 10,000 or 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 can a kind use separately, also can use simultaneously more than 2 kinds or 2 kinds.
The addition of above-mentioned gelating agent, there is no particular limitation, can suitably select according to purpose, be 15 quality % or below the 15 quality % preferably with respect to the total amount of the resin in the oil phase, be more preferably 5～10 quality %.
-oxidation inhibitor-
Above-mentioned oxidation inhibitor, there is no particular limitation, can from known substances, suitably select, can enumerate, for example, 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 can a kind use separately, also can use simultaneously more than 2 kinds or 2 kinds.
Preferred 2 quality % of the addition of above-mentioned oxidation inhibitor in above-mentioned oil phase or below the 2 quality %, preferred especially 0.1～1.0 quality %.
-filler pigment-
For preventing in printing ink infiltration, adjust viscosity, above-mentioned filler pigment can be added in oil phase, water or the two-phase, and any one of preferred inorganic particles and organic fine particles.As above-mentioned inorganic particles, can enumerate, for example, carclazyte, silicon-dioxide, talcum, clay, lime carbonate, barium sulfate, titanium oxide, aluminium are white, 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 %.
＜water 〉
Above-mentioned water contains water, tinting material, water-soluble high-molecular compound, water-miscible organic solvent, ionogen, O/W resin emulsion, sanitas or mould inhibitor, pH adjustment agent etc. and forms.
As above-mentioned water, so long as clean getting final product, there is no particular limitation, can suitably select according to purpose, for example, can use tap water, ion exchanged water, distilled water etc.
-tinting material-
As above-mentioned tinting material, can use the water-insoluble tinting material such as known pigment, dispersed dye of various tones.
As above-mentioned water-insoluble tinting material, can enumerate, for example, carbon black classes such as acetylene black, channel black, furnace black; Metal powder such as aluminium powder, bronze powder; Azo class pigment such as mineral dyes such as red iron oxide, chrome yellow, ultramarine, chromic oxide, titanium oxide, insoluble azo colour, azo lake pigment, condensed azo-pigment; Phthalocyanine pigment such as metal-free phthalocyanine, copper phthalocyanine; Condensation polycyclic class pigment such as anthraquinone pigments, quinoline a word used for translation ketone pigment, isoindoline ketone pigment, isoindoline class pigment, dioxazine (ジ オ キ サ Application ジ Application) class pigment, intellectual circle's class pigment, perylene class pigment, perylene ketone (ペ リ ノ Application) class pigment, thioindigo class pigment, quinophthalone class pigment, metal complex; The pigment dyestuffs such as color lake of acidity or basic dyestuff; Oil-soluble colourant such as diazotizing dyes, anthraquinone dyes; High-visibility pigment etc.These can a kind use separately, also can use simultaneously more than 2 kinds or 2 kinds.
As above-mentioned high-visibility pigment, be when block polymerization synthetic resin or after the polymerization, dissolving or the painted fluorescence dye that sends various colors, the painted block resin that pulverizing obtains and carry out the material of the so-called synthetic resins sosoloid type of miniaturization, synthetic resins as carried dye, can enumerate, for example, melamine resin, urea resin, sulfonamide resin, Synolac, polyvinyl chloride (PVC) RESINS etc.
Carbon black as above-mentioned tinting material, can use commercially available product, can enumerate, for example, MA-100, MA-7, MA-77, MA-11, #40, #44 (being Mitsubishi chemical Co., Ltd's system), Ravenl100, Raven 1080, Raven 1255, Raven 760, Raven 410 (being コ ロ Application PVC ヤ Application カ one ボ Application society system) etc.
There is no particular limitation for the median size of above-mentioned tinting material, can suitably select according to purpose, preferred 0.001～0.1 μ m, more preferred 0.01～0.1 μ m.
There is no particular limitation for the addition of above-mentioned tinting material in emulsified ink for porous printing, can suitably select according to purpose, usually preferred 2～15 quality %.
-water-soluble high-molecular compound-
There is no particular limitation as above-mentioned water-soluble high-molecular compound, can suitably select from known substances, can enumerate, for example, natural high moleculer eompound, semi-synthetic macromolecular compound, synthetic macromolecular compound etc.
As above-mentioned natural high moleculer eompound, can enumerate, for example, 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, can enumerate, for example, carboxymethyl cellulose, methylcellulose gum, Natvosol, hydroxypropylcellulose, Vltra tears, hydroxymethyl starch, carboxymethyl starch, dialdehyde starch etc.
As above-mentioned synthetic macromolecular compound, can enumerate, for example, 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 % at the preferred 25 quality % of the addition of above-mentioned aqueous phase or below the 25 quality %.
-water-miscible organic solvent-
Above-mentioned water-miscible organic solvent can be used as the evaporation of water inhibitor or frostproofer suitably adds.As this water-miscible organic solvent, have no particular limits, can from known substances, suitably select, can enumerate, for example, rudimentary saturated monohydroxy alcohol, glycol, polyvalent alcohol etc.These can use a kind separately, also can use simultaneously more than 2 kinds or 2 kinds.
As above-mentioned rudimentary saturated monohydroxy alcohol, can enumerate, for example, methyl alcohol, ethanol, Virahol, butanols, isopropylcarbinol etc.As above-mentioned glycol, can enumerate, for example, ethylene glycol, glycol ether, propylene glycol etc.Can enumerate as above-mentioned polyvalent alcohol, for example, glycerine, Sorbitol Powder etc.
Among these,, preferably use boiling point: glycerine (boiling point: 290 ℃) at the water-miscible organic solvent more than 220 ℃ or 220 ℃, for example from preventing the viewpoint of the dry set of tinting material on printing press.
Above-mentioned water-miscible organic solvent is more preferably 4～12 quality % at preferred 1～15 quality % of the addition of above-mentioned aqueous phase, preferred especially 5～9 quality %.
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 negatively charged ion or cationic a kind of above-mentioned ionic salt that contains at least can be enumerated, for example, and 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 can use a kind separately, also can use simultaneously more than 2 kinds or 2 kinds.
Above-mentioned ionogen is more preferably 0.5～1.5 quality % at preferred 0.1～2 quality % of the addition of above-mentioned aqueous phase.
As above-mentioned oil-in-water-type (O/W) resin emulsion, have no particular limits, can from known substances, suitably select, can be that synthetic macromolecular compound also can be a natural high moleculer eompound.
As above-mentioned synthetic macromolecular compound, can enumerate, for example, 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 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 can use a kind separately, also can use simultaneously more than 2 kinds or 2 kinds.
In addition, the dispersing method for above-mentioned oil-in-water-type resin emulsion also has no particular limits, and can add dispersion agent, protective colloid, tensio-active agent, in addition, also can be by the emulsifier-free emulsion polymerization synthetic.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 ℃ or 40 ℃.
Foregoing preservatives or mould inhibitor add in order to prevent bacterium or mould from breeding in emulsion, are effective when preserving emulsion for a long time.As this sanitas or mould inhibitor, have no particular limits, can use the material of from known substances, suitably selecting, can enumerate, for example, aromatic hydroxy compound such as Whitfield's ointment, phenols, methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate or their muriate, Sorbic Acid, dehydro-acetic acid etc.These can use a kind separately, also can use simultaneously more than 2 kinds or 2 kinds.
Foregoing preservatives or mould inhibitor are more preferably 0.1～1.2 quality % at the preferred 3 quality % of the addition of above-mentioned aqueous phase or below the 3 quality %.
Adjust agent as above-mentioned pH, have no particular limits, can from known substances, suitably select to use, can suitably enumerate, for example, 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.
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, add rust-preventive agent or defoamer to aqueous phase, in the time of can preventing to print, printing press be owing to printing ink gets rusty, or printing ink bubbles.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.
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 modulating 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, mixing oil composition, dispersion agent, resin and emulsifying agent stir by high speed dissolver.Afterwards, carry out dispersion treatment, the modulation oil phase with sand mill (LMZ2, ア シ ザ ワ Off ア イ Application テ Star Network Co., Ltd. system).On the other hand, mixed colorant, water-soluble polymer, dispersion agent, frostproofer and sanitas are dissolved in water well with this mixed solution, the modulation 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.
As described above, emulsified ink for porous printing of the present invention, can improve with the water-insoluble tinting material add to printing ink that aqueous phase obtains after placement since the mesh that the set of insoluble tinting material causes stop up, and therefore airborne shelf-stability excellence goes for for example changeing the porous printing that porous printer carries out with wheel.
By the present invention, can provide and to solve the problems that in the past existed, can improve with the water-insoluble tinting material add to printing ink that aqueous phase obtains after placement because the mesh that the set of insoluble tinting material causes stops up and the water-in-oil-type of airborne shelf-stability excellence (w/o type) emulsified ink for porous printing.
Below, embodiments of the invention are described, but the present invention is not subjected to any qualification of these embodiment.
(embodiment 1)
The modulation of-emulsified ink for porous printing-
At first, prescription mixing oil composition, dispersion agent, resin and emulsifying agent according to table 1 record stir by high speed dissolver.Afterwards, carry out dispersion treatment, the modulation oil phase with sand mill (LMZ2, ア シ ザ ワ Off ア イ Application テ Star Network Co., Ltd. system).
In addition, prescription mixed colorant, water-soluble polymer, dispersion agent, frostproofer and sanitas according to table 1 record are dissolved in water well with this mixed solution, the modulation water.
Then, use mulser (daylight ケ ミ カ Le ズ Co., Ltd. system, emulsification experimental 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 2～9)
The modulation of-emulsified ink for porous printing-
In embodiment 1, except that changing to the composition shown in table 1 and the table 2, similarly to Example 1, make the emulsified ink for porous printing of embodiment 2～9.
(comparative example 1～2)
The modulation of-emulsified ink for porous printing-
In embodiment 1, except that changing to the composition shown in the table 2, similarly to Example 1, make the emulsified ink for porous printing of comparative example 1 and 2.
[table 1]
| Composition (quality %) | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |||
| Oil phase | Mineral oil | サンセン310 | サ Application oil society system | 20.0 | 20.0 | 20.0 | 20.0 | 20.0 |
| サンセン420 | サ Application oil society system | 5.9 | 5.6 | 5.2 | 5.2 | 5.6 | ||
| The AF-6 solvent | Nippon Oil(Nippon Mitsubishi Oil) society system | - | - | - | - | - | ||
| Vegetables oil | The soybean oil methyl esters | When flourish ケ ミ カ Le society system | - | - | - | - | - | |
| Soybean oil | Day is food society system clearly | - | - | - | - | - | ||
| Colorant dispersion | OTP-75 | Daylight ケ ミ カ Le ズ society system | 0.1 | - | - | - | - | |
| ブレンアクトAL-M | Monosodium glutamate Off ア イ Application テ Network ノ society system | - | 0.4 | 0.4 | 0.4 | - | ||
| アジスバ-PN411 | Monosodium glutamate Off ア イ Application テ Network ノ society system | - | - | 0.4 | 0.4 | - | ||
| Sospers5000 | LUBRIZOL society system | - | - | - | - | - | ||
| Sospers13940 | LUBRIZOL society system | - | - | - | - | 0.4 | ||
| Sospers16000 | LUBRIZOL society system | - | - | - | - | - | ||
| Resin | Ha リ Off エ ノ-Le 173 (Mw:6 ten thousand) | Ha リ マ changes into society's system | - | - | - | - | - | |
| The soybean oil Synolac | Waste Chuan Huaxuegongyeshe system | - | - | - | - | - | ||
| Emulsifying agent | Sorbitan monooleate | Japan grease society system | 4.0 | 4.0 | 4.0 | 4.0 | 4.0 | |
| Oil phase adds up to (quality %) | 30.0 | 30.0 | 30.0 | 30.0 | 30.0 | |||
| Water | Tinting material | RAVEN760 | コ ロ Application PVC ヤ Application カ-ボ Application society system | 7.0 | 7.0 | 7.0 | 7.0 | 7.0 |
| Water-soluble polymer | Polyvinylpyrolidone (PVP) (K-30) | BASF society system | 7.0 | 7.0 | 7.0 | 7.0 | 7.0 | |
| Colorant dispersion | NP-15 | Daylight ケ ミ カ Le ズ society system | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | |
| Water | Ion exchanged water | 48.7 | 48.7 | 48.7 | 48.7 | 48.7 | ||
| Water-miscible organic solvent | Ethylene glycol | Mitsui Chemicals society system | 7.0 | 7.0 | 7.0 | - | - | |
| Glycerine | Japan grease society system | - | - | - | 7.0 | 7.0 | ||
| Sanitas | Methyl p-hydroxybenzoate | Northeast chemistry society system | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | |
| Water adds up to (quality %) | 70.0 | 70.0 | 70.0 | 70.0 | 70.0 | |||
| Add up to (quality %) | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | |||
[table 2]
| Composition (quality %) | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Comparative example 1 | Comparative example 2 | |||
| Oil phase | Mineral oil | サンセン310 | サ Application oil society system | 20.0 | 22.0 | 20.0 | 15.4 | 20.0 | 20.0 |
| サンセン420 | サ Application oil society system | 5.6 | 2.0 | 5.4 | - | 6.0 | 6.0 | ||
| The AF-6 solvent | Nippon Oil(Nippon Mitsubishi Oil) society system | - | - | - | 3.0 | - | - | ||
| Vegetables oil | The soybean oil methyl esters | When flourish ケ ミ カ Le society system | - | - | - | 2.0 | - | - | |
| Soybean oil | Day is food society system clearly | - | - | - | 2.0 | - | - | ||
| Colorant dispersion | OTP-75 | Daylight ケ ミ カ Le ズ society system | - | - | - | - | - | - | |
| ブレンアクトAL-M | Monosodium glutamate Off ア イ Application テ Network ノ society system | - | - | - | - | - | - | ||
| アジスバ-PN411 | Monosodium glutamate Off ア イ Application テ Network ノ society system | - | - | - | - | - | - | ||
| Sospers5000 | LUBRIZOL society system | - | - | 0.2 | 0.2 | - | - | ||
| Sospers13940 | LUBRIZOL society system | - | - | - | - | - | - | ||
| Sospers16000 | LUBRIZOL society system | 0.4 | 2.0 | 0.4 | 0.4 | - | - | ||
| Resin | Ha リ Off エ ノ-Le 173 (Mw:6 ten thousand) | Ha リ マ changes into society's system | - | - | - | 1.0 | - | - | |
| The soybean oil Synolac | Waste Chuan Huaxuegongyeshe system | - | - | - | 2.0 | - | - | ||
| Emulsifying agent | Sorbitan monooleate | Japan grease society system | 4.0 | 4.0 | 4.0 | 6.0 | 4.0 | 4.0 | |
| Oil phase adds up to (quality %) | 30.0 | 30.0 | 30.0 | 30.0 | 30.0 | 30.0 | |||
| Water | Tinting material | RAVEN760 | コ ロ Application PVC ヤ Application カ-ボ Application society system | 7.0 | 7.0 | 7.0 | 8.0 | 7.0 | 7.0 |
| Water-soluble polymer | The polyvinyl pyrrole is alkane ketone (K-30) slightly | BASF society system | 7.0 | 7.0 | 7.0 | 3.5 | 7.0 | 7.0 | |
| Colorant dispersion | NP-15 | Daylight ケ ミ カ Le ズ society system | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | - | |
| Water | Ion exchanged water | 48.7 | 48.7 | 48.7 | 44.2 | 48.7 | 48.9 | ||
| Water-miscible organic solvent | Ethylene glycol | Mitsui Chemicals society system | - | - | - | - | 7.0 | 7.0 | |
| Glycerine | Japan grease society system | 7.0 | 7.0 | 7.0 | 12.0 | - | - | ||
| Sanitas | Methyl p-hydroxybenzoate | Northeast chemistry society system | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | |
| Water adds up to (quality %) | 70.0 | 70.0 | 70.0 | 68.0 | 70.0 | 70.0 | |||
| Add up to (quality %) | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | |||
Below, each emulsified ink for porous printing that obtains is estimated airborne shelf-stability in accordance with the following methods.The results are shown in table 3.
＜airborne shelf-stability 〉
The evaluation of airborne shelf-stability, the viscosity of estimating when placing printing ink under the high temperature open state changes as substituting evaluation.Printing ink is contained in the vessel, with open state, preserved for 1 week down at 60 ℃, with 5 grades of evaluations, compare with the viscosity before the placement, what discovery viscosity significantly rose is evaluated as 1, and that does not find the viscosity rising is evaluated as 5.In addition, the result represents with the mean value of 3 mensuration.
[table 3]
| Embodiment | Comparative example | ||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 1 | 2 | |
| Under 60 ℃ of open states, place 96 hours viscosity rising (grade) | 3.0 | 3.0 | 3.5 | 4.0 | 4.5 | 4.5 | 4.5 | 5.0 | 5.0 | 1.0 | 1.0 |
Can confirm that from the result of table 3 comparative example 1 is not owing to contain dispersion agent in the oil phase, airborne shelf-stability is poor.In addition, comparative example 2 is not because any one of oil phase and water all added dispersion agent, and therefore airborne shelf-stability is poor.
With respect to this, embodiment 1～9 compares with 2 with comparative example 1, can confirm airborne shelf-stability excellence.In addition, from the result of embodiment 4 and embodiment 5～7, can confirm to use the superiority of polyesteramine compounds as dispersion agent.
In addition, from the result of embodiment 6 and embodiment 8, can confirm in oil phase, to add the superiority of ammonium substituted phthalocyanine sulfonic acid class dispersion agent.
In addition, from the result of embodiment 3 and embodiment 4, can confirm to add as the superiority (boiling point of ethylene glycol be 197 ℃) of boiling point at the glycerine (290 ℃ of boiling points) of the water-miscible organic solvent more than 220 ℃ or 220 ℃ at aqueous phase.
Emulsified ink for porous printing of the present invention, can improve with the water-insoluble tinting material add to printing ink that aqueous phase obtains after placement since the mesh that the set of insoluble tinting material causes stop up, and therefore airborne shelf-stability excellence goes for for example changeing the porous printing that porous printer carries out with wheel.
Claims (10)
1. an emulsified ink for porous printing is characterized in that, this printing ink contains oil phase 10～90 quality % and water 90～10 quality %, and only add tinting material to this aqueous phase, wherein, contain the water-insoluble tinting material, and in above-mentioned oil phase, contain dispersion agent at this aqueous phase.
2. according to the emulsified ink for porous printing of claim 1 record, wherein, aqueous phase also contains dispersion agent.
3. the emulsified ink for porous printing of putting down in writing according to claim 1, wherein, the dispersion agent in the oil phase is the polyesteramine compounds.
4. the emulsified ink for porous printing of putting down in writing according to claim 1, wherein, the dispersion agent in the oil phase is an ammonium substituted phthalocyanine sulfonic acid class dispersion agent.
5. the emulsified ink for porous printing of putting down in writing according to claim 1, wherein, the water-insoluble tinting material is a pigment.
6. the emulsified ink for porous printing of putting down in writing according to claim 5, wherein, pigment is any one in carbon black and the phthalocyanine pigment.
7. the emulsified ink for porous printing of putting down in writing according to claim 1, wherein, the addition of dispersion agent is 40 mass parts or below 40 mass parts with respect to water-insoluble tinting material 100 mass parts.
8. the emulsified ink for porous printing of putting down in writing according to claim 1, wherein, it is water-miscible organic solvent more than 220 ℃ or 220 ℃ that aqueous phase contains boiling point.
9. the emulsified ink for porous printing of putting down in writing according to claim 8, wherein, boiling point is that the water-miscible organic solvent more than 220 ℃ or 220 ℃ is a glycerine.
10. the emulsified ink for porous printing of putting down in writing according to claim 1 wherein, contains the soya fatty acid Synolac in the oil phase.
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| JP2004312309A JP2006124464A (en) | 2004-10-27 | 2004-10-27 | Emulsion ink for screen printing |
| JP312309/04 | 2004-10-27 |
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| JP5315780B2 (en) * | 2008-05-12 | 2013-10-16 | 株式会社リコー | Emulsion ink for stencil printing |
| CN103328588B (en) * | 2010-10-28 | 2015-08-19 | 深圳智慧天使投资有限公司 | A kind of W/O emulsion ink composition and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0638615A2 (en) * | 1993-08-10 | 1995-02-15 | Toyo Ink Manufacturing Co., Ltd. | Process for the production of copper phthalocyanine pigment and its use |
| CN1123296A (en) * | 1994-07-25 | 1996-05-29 | 理想科学工业株式会社 | Emulsion ink for stencil printing |
| CN1239124A (en) * | 1998-04-27 | 1999-12-22 | 东北理光株式会社 | Water-in-oil emulsion ink for porous printing |
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| JP3008724B2 (en) * | 1993-04-09 | 2000-02-14 | 東洋インキ製造株式会社 | Ink for stencil printing |
| JP3725921B2 (en) * | 1995-10-24 | 2005-12-14 | 東北リコー株式会社 | Emulsion ink for stencil printing |
| JPH10316919A (en) * | 1997-05-16 | 1998-12-02 | Ricoh Co Ltd | Emulsion ink, stencil printing process using the same and multicolor printing stencil printing machine |
| JP4112101B2 (en) * | 1998-12-01 | 2008-07-02 | 東北リコー株式会社 | Emulsion ink for stencil printing |
| JP4080121B2 (en) * | 1999-06-03 | 2008-04-23 | 東北リコー株式会社 | Water-in-oil emulsion ink for stencil printing |
| JP4322391B2 (en) * | 2000-03-23 | 2009-08-26 | 東北リコー株式会社 | W / O emulsion ink for stencil printing |
| JP4777525B2 (en) * | 2001-03-05 | 2011-09-21 | 東北リコー株式会社 | W / O emulsion ink for stencil printing |
| JP2003026979A (en) * | 2001-07-13 | 2003-01-29 | Tohoku Ricoh Co Ltd | W/o emulsion ink for stencil printing |
| JP3930350B2 (en) * | 2002-03-14 | 2007-06-13 | 東北リコー株式会社 | W / O emulsion ink for stencil printing |
| JP2004182864A (en) * | 2002-12-03 | 2004-07-02 | Tohoku Ricoh Co Ltd | W/o type emulsion ink for stencil printing |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0638615A2 (en) * | 1993-08-10 | 1995-02-15 | Toyo Ink Manufacturing Co., Ltd. | Process for the production of copper phthalocyanine pigment and its use |
| CN1123296A (en) * | 1994-07-25 | 1996-05-29 | 理想科学工业株式会社 | Emulsion ink for stencil printing |
| CN1239124A (en) * | 1998-04-27 | 1999-12-22 | 东北理光株式会社 | Water-in-oil emulsion ink for porous printing |
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