CN1690139A - Emulsified ink for stencil printing - Google Patents
Emulsified ink for stencil printing Download PDFInfo
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- CN1690139A CN1690139A CN 200510053002 CN200510053002A CN1690139A CN 1690139 A CN1690139 A CN 1690139A CN 200510053002 CN200510053002 CN 200510053002 CN 200510053002 A CN200510053002 A CN 200510053002A CN 1690139 A CN1690139 A CN 1690139A
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Abstract
To provide an emulsion ink for use in stencil printing without demerits such as clogging after standing and retardation of image rising in printing and capable of sharply improving staining caused by a feed roller upon two sides printing.
Description
Technical field
The present invention relates to the emulsified ink for porous printing of a kind of water-in-oil-type (w/o type), the bad phenomenon that image occur to postpone in plug-hole after this printing ink is not placed or the printing, and the paper-feed roll when improving two-face printing significantly pollutes.
Background technology
Up to now, stencil printing method is to adopt the porous printing body paper (hole version) with perforated portion, and the perforated portion by this hole version moves by side to opposite side with printing ink from one of hole version, is printed at paper etc. thus and carries out method of printing on the thing surface.In this stencil printing method, use for porous printing printing ink of water-in-oil-type (w/o type), contain (references such as volatile solvent, nonvolatile solvent, resin, tinting material, tensio-active agent, water, frostproofer, ionogen, gelating agent and sanitas in this printing ink, for example, Te Kaiping 5-117565 communique, the spy opens flat 5-117564 communique).
, in the two-face printing that adopts porous printer, exist so-called paper-feed roll generation pollution problems.This paper-feed roll pollutes and refers to, when two-face printing, ink transfer on the image in the 1st printing (to the printing with the paper surface) is used on the paper paper-feed roll to printing press, and when the 2nd printing (to printing) with the paper back side, the printing ink that carries out the 1st printing of following the 2nd printing transfer to conversely from the paper-feed roll image make the image dirt phenomenon.This occasion, on porous printer, the drying of printing ink depends on that printing ink to the soaking into of paper, compares with other print systems, exsiccant is slow, so and the printing ink epithelium on the image weak be the serious reason of paper-feed roll pollution problem.
In addition, in recent years, consider, improved the necessity of two-face printing in order to reduce paper using amount from the viewpoint of environmental protection, and for porous printer, the also more and more improvement of strong request paper-feed roll pollution.
Yet, for the improvement that above-mentioned paper-feed roll pollutes, once attempted seeking pigment is improved the wetting-out rate of paper or pigment being improved to the anchorage of paper by adding varnish etc. by improving pigment-dispersing, but the effect that all not have acquisition to substantially improve.
Therefore, still do not obtain at present, after the placement not plug-hole or the paper-feed roll when not having bad phenomenon, the two-face printing of the delay that the image in the printing occurs pollute the emulsified ink for porous printing that can improve significantly, therefore wish apace it to be developed.
The general introduction of invention
The object of the present invention is to provide a kind of emulsified ink for porous printing, the bad phenomenon of the delay that the image in plug-hole after this printing ink is not placed or the printing occurs, paper-feed roll pollutes and has improved ink stability when high temperature is preserved when improving two-face printing significantly.
Obtained following discovery for solving the result that the above-mentioned problem inventor furthers investigate repeatedly.Be that described discovery is, in the emulsified ink for porous printing by oil phase 10～90 quality % and water 90～10 quality % formation, remove and contain oil phase 10～90 quality % and water 90～10 quality %, also in this oil phase, contain pigment as tinting material, and also the K value that contains 1.0～6.0 quality % with respect to the total mass of above-mentioned water by solid component meter at this aqueous phase is equal to or less than 30 Polyvinylpyrolidone (PVP), the delay that image in plug-hole after can not placing thus or the printing occurs, and the paper-feed roll can improve two-face printing significantly the time pollutes.
The present invention is that the inventor finishes based on above-mentioned discovery, and is as follows as the measure that solves above-mentioned problem.That is,
＜1〉is emulsified ink for porous printing, it is characterized in that, remove and contain oil phase 10～90 quality % and water 90～10 quality %, also in this oil phase, contain pigment, be equal to or less than 30 Polyvinylpyrolidone (PVP) but also contain the K value of counting 1.0～6.0 quality % by solids component with respect to the total mass of above-mentioned water at this aqueous phase as tinting material.For this＜1 described in emulsified ink for porous printing, pollute in order to improve paper-feed roll, as the pigment of tinting material, preferred surface tension force is low and be present in paper is soaked into fast oil phase side.In addition, the film forming properties owing to this Polyvinylpyrolidone (PVP) when the aqueous phase of emulsified ink adds Polyvinylpyrolidone (PVP) can make the printing ink epithelium that forms image tough, so can prevent the generation that paper-feed roll pollutes.In addition, owing to make the addition of Polyvinylpyrolidone (PVP) count 1.0～6.0 quality % by solids component with respect to the total mass of above-mentioned water, the plug-hole that the curing of silk screen when emulsified ink is put into rotary drum or the Polyvinylpyrolidone (PVP) on the version body causes does not then take place, so can print well.
＜2〉be above-mentioned＜1〉described in emulsified ink for porous printing, wherein the K value of Polyvinylpyrolidone (PVP) is 15～30.
＜3〉be above-mentioned＜1〉described in emulsified ink for porous printing, wherein pigment is phthualocyanine pigment.In above-mentioned＜2〉described in emulsified ink for porous printing in, when using phthualocyanine pigment, its advantage is, the interpolation by Polyvinylpyrolidone (PVP) prevents that the effect that paper-feed roll pollutes is big.Promptly, when in the porous printer two-face printing, using phthualocyanine pigment as tinting material, this phthalocyanine pigment particle is flaky, pigment-dispersing is than other aberration, poor to the impregnability of paper and residual other pigment of paper-feed roll damage ratio that make of paper on image surface residue are remarkable in blue oil China ink in emulsified ink or the green oil China ink, but by adding Polyvinylpyrolidone (PVP), these problems can be eliminated, thereby the effect that paper-feed roll pollutes can be efficiently prevented.
＜4〉be above-mentioned＜1 that aqueous phase contains glycerine〉described in emulsified ink for porous printing.Should＜4〉described in emulsified ink for porous printing in, even the delay phenomenon of considering to make the addition optimizing of Polyvinylpyrolidone (PVP) also to have the printed images after the placement to occur from the viewpoint that prevents plug-hole as mentioned above.But by then can improve the problem of the delay of printed images appearance toward aqueous phase interpolation glycerine because of the good performance of keeping humidity of this glycerine.
＜5〉be above-mentioned＜4〉described in emulsified ink for porous printing, wherein with respect to the total mass of water, the content of glycerine is 3.0～15.0 quality %.
＜6〉be above-mentioned＜1 of aqueous phase sulfur acid magnesium〉described in emulsified ink for porous printing.Should＜6〉described in emulsified ink for porous printing in, by adding sal epsom toward aqueous phase, ink oil is separated or water sepn in the time of then can preventing the high temperature preservation, thereby can improve ink stability, and when the container from the charge of oil China ink takes off lid, can printing ink not hung, thereby the undesirable situation such as floor or carpet pollution that can prevent well takes place by mistake.
The description of preferred embodiment
Emulsified ink for porous printing of the present invention, remove and contain oil phase 10～90 quality % and water 90～10 quality %, also in this oil phase, contain pigment as tinting material, be equal to or less than 30 Polyvinylpyrolidone (PVP) but also contain the K value of counting 1.0～6.0 quality % by solids component with respect to the total mass of above-mentioned water, also contain other compositions in addition as required at this aqueous phase.
This occasion as above-mentioned emulsified ink for porous printing, preferably contains oil phase 10～90 quality % and water 90～10 quality %, more preferably contains oil phase 20～40 quality % and water 60～80 quality %.
When the ratio of mixture of above-mentioned oil phase was lower than 10 quality %, ink stability was poor, and water sepn particularly takes place sometimes easily, and when surpassing 90 quality %, ink stability is poor, particularly takes place separating of oil sometimes easily.
＜water 〉
-Polyvinylpyrolidone (PVP)-
As above-mentioned Polyvinylpyrolidone (PVP) (PVP), have no particular limits, can from known product, select aptly, also can be commercially available product, can also be suitable synthetic product.These can use a kind separately, also can more than 2 kinds or 2 kinds and use.
As the commercially available product of above-mentioned Polyvinylpyrolidone (PVP), for example, can enumerate the Le PVC テ Star Network K17 of BASF society system, PVP シ リ-ズ of Le PVC テ Star Network K30, ア イ エ ス ピ-ジ ヤ パ Application society system or the like.
As above-mentioned Polyvinylpyrolidone (PVP) (PVP), for example, can enumerate with following structural formula (1) signifier to preferred.
In the said structure formula (1), n represents the polymerization degree.
K value as above-mentioned Polyvinylpyrolidone (PVP) preferably is equal to or less than 30, and more preferably 15～30.Here, described K value, be numerical value as the molecular-weight average of weighing Polyvinylpyrolidone (PVP), the polymerization degree, limiting viscosity, the K value was less than 15 o'clock, the effect of polluting for paper-feed roll that prevents dies down, and surpass at 30 o'clock, and the viscosity of water becomes too high, and ink viscosity also uprises so hinder from the printing ink bag sucking-off sometimes or the paper when printing soaks into.
Above-mentioned K value can derive from the viscosimetric analysis value of Polyvinylpyrolidone (PVP), and can calculate based on the Fikentscher formula of following mathematical expression 1.
＜mathematical expression 1 〉
K＝1000K
0
In the above-mentioned mathematical expression 1, c represents the concentration in the g/100ml solution.η rel represents the viscosity with solvent ratio solution.
As the content of Polyvinylpyrolidone (PVP) in the emulsified ink for porous printing, press preferred 1.0～6.0 quality % of solid component meter, more preferably 1.4～3.0 quality % with respect to the total mass of above-mentioned water.Above-mentioned content does not prevent effect for what paper-feed roll polluted during less than 1.0 quality %, even surpass 6.0 quality % not than the effect of its also high anti-paper-feed roll pollution, cost is uprised yet.In addition, plug-hole when placing, rotary drum takes place sometimes.
Above-mentioned aqueous phase can also add above-mentioned Polyvinylpyrolidone (PVP) other water-soluble high-molecular compounds in addition as required.As these other water-soluble high-molecular compounds, have no particular limits, can from known water-soluble high-molecular compound, suitably select according to purpose, for example, can enumerate natural high moleculer eompound, semi-synthetic macromolecular compound, synthetic macromolecular compound, etc.These can use a kind separately, also can more than 2 kinds or 2 kinds and use.
As above-mentioned natural high moleculer eompound, for example, can enumerate starch, mannosans, sodium alginate, Polygalactan, tragacanth gum, Sudan Gum-arabic, pullulan, dextran, xanthan gum, gelatine, gelatin, collagen, casein etc.
As semi-synthetic macromolecular compound, for example, can enumerate carboxymethyl cellulose, methylcellulose gum, Natvosol, hydroxypropylcellulose, Vltra tears, hydroxymethyl starch, carboxymethyl starch, dialdehyde starch etc.
As synthetic macromolecular compound, for example, can enumerate acrylic resin derivatives such as polyacrylic acid, sodium polyacrylate, polyacrylic acid trolamine; Polyvinyl alcohol, polyacrylamide, polyoxyethylene, polyvinyl methyl ether etc.
As the content of above-mentioned water-soluble high-molecular compound in printing ink (still, comprise Polyvinylpyrolidone (PVP)), there is no particular limitation, can suitably select according to purpose, preferably with respect to the total mass of above-mentioned water, count 25 quality % or below the 25 quality % by solids component, more preferably 1.0～15 quality %.
At above-mentioned aqueous phase, except that above-mentioned Polyvinylpyrolidone (PVP) and other water-soluble high-molecular compounds, in the scope that not anti-evil emulsion forms, water, evaporation of water inhibitor or frostproofer, ionogen, O/W resin emulsion, sanitas or mould inhibitor, pH regulator agent etc. can also be contained, other compositions can also be contained as required.
As above-mentioned water, so long as peace and quiet then do not have a special restriction, can suitably select according to purpose, for example, can use tap water, ion exchanged water, distilled water etc.
As above-mentioned evaporation of water inhibitor or frostproofer, have no particular limits, can from known material, suitably select to use, for example, can enumerate rudimentary saturated monohydroxy alcohol, dibasic alcohol, polyvalent alcohol etc.These can use a kind separately, also can more than 2 kinds or 2 kinds and use.
As above-mentioned rudimentary saturated monohydroxy alcohol, for example, can enumerate methyl alcohol, ethanol, Virahol, butanols, isopropylcarbinol etc.As above-mentioned dibasic alcohol, for example, can enumerate ethylene glycol, Diethylene Glycol, propylene glycol etc.As above-mentioned polyvalent alcohol, for example, can enumerate glycerine, Sorbitol Powder etc.
Wherein, to improve aspect glycerine be particularly preferred having excellent moisture retention and seek delay that printed images occurs.
As the addition of above-mentioned glycerine, with respect to the total mass of water, preferred 3.0～15.0 quality %, more preferably 6.0～12 quality %.The addition of above-mentioned glycerine is during less than 3.0 quality %, the effect that does not have glycerine to add, and when surpassing 15.0 quality %, the excess stickiness ground of water is risen, and slack-off to soaking into of paper, unfavorable to preventing the paper-feed roll pollution.
As above-mentioned ionogen, add the preferred ionogen that constitutes by the high ion of lyotrope (suitable) preface of effective raising emulsion permanence that adds for improving stability of emulsion.As the high negatively charged ion of above-mentioned lyotrope (suitable) preface, for example, can enumerate citrate ions, tartrate ion, sulfate ion, acetic acid ion etc.On the other hand,, for example, can enumerate alkalimetal ion, alkaline-earth metal ion etc. as the high positively charged ion of above-mentioned lyotrope (suitable) preface.As above-mentioned ionogen, preferred negatively charged ion at least or positively charged ion one side are the salt that above-mentioned ion constitutes.Therefore, as above-mentioned ionogen, for example, can enumerate sal epsom, sodium sulfate, Trisodium Citrate, sodium hydrogen phosphate, Sodium Tetraborate, sodium-acetate etc. for preferred.These can use a kind separately, also can more than 2 kinds or 2 kinds and use.
In the middle of these, when obtaining to prevent that high temperature from preserving separating of oil or water sepn, the raising ink stability of printing ink, prevent from especially preferably to add sal epsom on the excellent effect that printing ink hangs.
As above-mentioned electrolytical addition, have no particular limits, can suitably select according to purpose, but with respect to the total mass of water, preferred 0.1～2 quality %, more preferably 0.5～1.5 quality %.Above-mentioned electrolytical addition can not get because of ionogen adds the ink stability effect that produces during less than 0.1 quality %, and when surpassing 2 quality %, can not improved by the effect of China ink stability again, and cost has been improved.
As above-mentioned oil-in-water-type resin emulsion, have no particular limits, can from known product, select for use aptly, promptly can be that synthetic macromolecular compound also can be a natural high moleculer eompound.As above-mentioned synthetic macromolecular compound, for example, can enumerate polyvinyl acetate resins, acrylate resin, methacrylate resin, polyvinyl chloride (PVC) RESINS, ethylene-vinyl acetate copolymer, vinyl acetate-acrylate multipolymer, 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 macromolecular compound that in emulsified ink for porous printing, can add in the general oil phase etc.These can use a kind separately, also can more than 2 kinds or 2 kinds and use.
In addition, also having no particular limits for the dispersing method of above-mentioned oil-in-water-type resin emulsion, can add dispersion agent, protective colloid, tensio-active agent, also can be by soap-free emulsion synthetic product in addition.Minimum film-forming temperature as above-mentioned oil-in-water-type resin emulsion has no particular limits, and can select according to purpose is suitable, but preferably be equal to or less than 40 ℃.
Foregoing preservatives or mould inhibitor add in order to prevent bacterium or mould from breeding in emulsion, are effective in the occasion of prolonged preservation emulsion.As this sanitas or mould inhibitor, have no particular limits, can from known material, suitably select to use, can enumerate, for example, aromatic hydroxy compound such as Whitfield's ointment, phenols, p-Para Hydroxy Benzoic Acid methyl esters, p-Para Hydroxy Benzoic Acid ethyl ester or its muriate, Sorbic Acid, dehydroacetic acid (DHA) etc.These can use a kind separately, also can more than 2 kinds or 2 kinds and use.
Addition as foregoing preservatives or mould inhibitor has no particular limits, and can suitably select according to purpose, but with respect to the total mass of water contained in the printing ink, preferably be equal to or less than 3 quality %, more preferably 0.1～1.2 quality %.
As above-mentioned pH regulator agent, have no particular limits, can from known material, suitably select to use, can enumerate, for example, trolamine, sodium-acetate, triamylamine etc.Adding the pH that these pH regulator agent can keep water as required is 6～8.When if the pH of water leaves above-mentioned scope, can suffer damage with its effect of water-soluble high-molecular compound occasion adding tackifier.
＜oil phase 〉
In the above-mentioned oil phase, contain pigment, in the scope that not overslaugh emulsion forms, can also contain other compositions such as colorant dispersion, resin, oxidation inhibitor, emulsifying agent, oil component, gelating agent, pigment extender as required as tinting material.
-tinting material-
As above-mentioned tinting material, have no particular limits, can from the known pigment of various tones, dispersed dye etc., select according to purpose.As above-mentioned tinting material, for example, can enumerate carbon black classes such as acetylene black, thermally oxidized black, furnace treated black; Metal powder such as aluminium powder, bronze powder; Azo pigments such as mineral dye, insoluble azo colour, azo lake pigment, condensed azo-pigment such as red iron oxide, lead and yellow-collation, group's cyanines, chromic oxide, titanium oxide; Phthualocyanine pigment such as metal-free phthalocyanine, copper phthalocyanine; Anthraquinone is a pigment, 2, and 3-quinoline a word used for translation ketone is that pigment, isoindoline ketone are that pigment, isoindoline are that pigment, diox piperazine is that pigment, intellectual circle are that pigment, perylene is that pigment, perylene ketone (ペ リ Le Application) is that pigment, thioindigo are that pigment, Kui phthalein ketone are condensation polycyclic series pigments such as pigment, metal complex; The pigment dyestuffs such as color lake of acidity or basic dyestuff; Oil-soluble colourant such as disazo dyes, anthraquinone based dye; High-visibility pigment or the like.These can use a kind separately, also can more than 2 kinds or 2 kinds and use.
In the middle of these, preferred above-mentioned pigment, preferred especially phthualocyanine pigment.Paper-feed roll takes place and pollutes in above-mentioned phthualocyanine pigment easily when the two-face printing of porous printer, the additive effect of Polyvinylpyrolidone (PVP) is remarkable.
As above-mentioned tinting material, when adding to carbon black in the oil phase, be lower than 5 acidic carbon black as pH, can use commercially available product, for example, can enumerate MA-100, MA-7, MA-77, MA-11, #40, #44 (being Mitsubishi chemical Co., Ltd's system), Raven1100, Raven1080, Raven1255, Raven760, Raven410 (being コ ロ Application PVC ア Application カ one ボ Application society system) etc.
Median size as above-mentioned tinting material has no particular limits, and can suitably select according to purpose, preferred 0.01～1.0 μ m, more preferably 0.01～0.5 μ m.
The addition of above-mentioned tinting material in emulsified ink for porous printing has no particular limits, and can suitably select according to purpose, usually preferred 2～15 quality %.
-colorant dispersion-
As above-mentioned colorant dispersion, so long as the material that not overslaugh emulsion forms then has no particular limits, can from known material, suitably select according to purpose, for example, can enumerate emulsifying agent nonionic surface active agent described below, alkylamine is a macromolecular compound, aluminum chelate, styrene-maleic anhydride copolymer, polyacrylic part alkyl ester, polyalkylene polyamine, the aliphatics polycarboxylic acid, polyethers, ester type aniorfic surfactant, the polycarboxylic long-chain amine salt of high molecular, polyamide-based compound, phosphoric acid ester is a tensio-active agent, alkyl sulfocarboxylic hydrochlorate, sulfonated, the dioctyl sulfosuccinate, polymine, alcohol amine salt etc., only otherwise the scope of overslaugh printing ink storage stability ionic surfactant then, amphotericses etc. can use.These can use a kind separately, also can more than 2 kinds or 2 kinds and use.
Addition as above-mentioned colorant dispersion has no particular limits, and can suitably select 40 quality % of preferred above-mentioned tinting material total mass or below the 40 quality %, more preferably 2～35 quality % according to purpose.
-resin-
Above-mentioned resin adds in order to improve tinting material and to be printed the set of thing, the dispersion of tinting material and the ageing stability of printing ink.As above-mentioned resin, have no particular limits, can from known resin, suitably select according to purpose, can enumerate, for example, rosin series resins such as rosin, 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; Synolac; Polymerized castor oil etc., in the middle of these, special preferred alcohols acid resin, modified rosin resin.These can use a kind separately, also can more than 2 kinds or 2 kinds and use.
As the addition of above-mentioned resin, consider 10 quality % of preferred printing ink total mass or below the 10 quality %, more preferably 1～7 quality % from printing ink cost and the suitable viewpoint of printing.
-emulsifying agent-
As mentioned emulsifier, then have no particular limits as long as can form the emulsifying agent of water-in-oil-type, can from known emulsifying agent, suitably select according to purpose, nonionic surface active agent is preferred especially.As this nonionic surface active agent, can enumerate, for example, sorbitan-fatty acid ester, glycerin fatty fat acid esters, polyglycerol fatty acid ester, propylene glycol fatty acid ester, pentaerythritol fatty ester, polyoxyethylene sorbitan fatty acid ester, the two sorbitan fatty acid esters of polyoxyethylene, 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 hardened castor oil, polyoxyethylene hydrous wool derivative, polyoxyethylene alkyl amine, the polyoxyethylene fatty acid acid amides, polyoxyethylene alkylphenyl formaldehyde condensation products etc.These can use a kind separately, also can more than 2 kinds or 2 kinds and use.
The addition of mentioned emulsifier in emulsified ink for porous printing has no particular limits, and can suitably select according to purpose, preferred 1～8 quality %, more preferably 2～5.5 quality %.
-oxidation inhibitor-
Above-mentioned antioxidant, the printing ink when preventing the oxidation of resin etc. and preventing in rotary drum long-term placement the rotten.As this oxidation inhibitor, have no particular limits, can from known oxidation inhibitor, suitably select to use according to purpose, can enumerate, for example, dihydro guaiac acid (NDGA), lignum-vitae fat, citrate, extraction tocopherol, tocopherol, butylhydroxy toluene, gallic acid, butylated hydroxytoluene, Tenox PG, butylated hydroxy anisole, sulfites, thiosulphate, xitix, ascorbate salt, ascorbic acid derivates etc. fall.These can use a kind separately, also can more than 2 kinds or 2 kinds and use.
Addition as above-mentioned oxidation inhibitor has no particular limits, and can suitably select according to purpose, with respect to total ink, preferably is equal to or less than 2 quality %, more preferably 0.1～1.0 quality %.
-oil component-
As above-mentioned oil component, have no particular limits, can from known oil, suitably select to use, can enumerate, for example, vegetables oil, mineral reserve thing wet goods.As above-mentioned vegetables oil, for example, can enumerate, soybean oil, Semen Maydis oil, sunflower oil, rape seed oil, Thistle oil, siritch, Semen Ricini oil, dehydrogenation Semen Ricini oil, camellia seed oil, sweet oil, Oleum Cocois, rice bran oil, Oleum Gossypii semen, plam oil, Semen Lini oil, palm kernel oil, tung oil, Camellia oil, raisin seed oil, desulfurization Prunus amygdalus oil, Pistacia vera oil (Pistacia vera oil), Jojoba oil, Macadamia ternifolia oil, virtue be nurse (メ De ウ ホ-system) wet goods suddenly.These can use a kind separately, also can more than 2 kinds or 2 kinds and use
As above-mentioned mineral oil, for example, can enumerate paraffin hydrocarbon system oil, cycloalkanes hydrocarbon system oil, oil series solvent, spindle oil, whiteruss, light oil, lam-oil, machine oil, gear oil, lubricating oil, motor wet goods.In the middle of these, preferred especially paraffin series oil, naphthene series oil, oil series solvent.
As above-mentioned paraffin hydrocarbon system oil, can use commercially available product, for example, can enumerate the day stone ス-パ-オ イ Le シ リ-ズ of the ガ of エ Network ソ Application モ-PVC Le society system-go イ Le ア-Network テ イ Star Network シ リ-ズ, Shin Nihon Oil Co., Ltd's system, the ダ イ ア Na プ ロ セ ス オ イ Le of Idemitsu Kosen Co., Ltd.'s system, ダ イ ア Na Off レ シ ア シ リ-ズ etc.
As above-mentioned cycloalkanes hydrocarbon system oil, preferably, adopt the carbon content (CN) of the naphthenic hydrocarbon composition of ring analysis to be equal to or greater than 30%, the carbon content of aromatic component (CA) is equal to or less than 20%, and the carbon content of paraffinic hydrocarbon composition (CP) is equal to or less than 55%, for example, the ガ of エ Network ソ Application モ-PVC Le society system-go イ Le ア-Network テ イ プ Network オ イ Le 155 and 300ID, ガ-go イ Le ア-Network テ イ Star Network オ イ Le ラ イ ト, ガ-go イ Le ア-Network テ イ Star Network オ イ Le C ヘ PVC-; The ダ イ ア Na プ ロ セ ス オ イ Le of Idemitsu Kosen Co., Ltd.'s system, ダ イ ア Na ア レ シ ア シ リ-ズ; The サ Application セ Application オ イ Le シ リ-ズ of Japan サ Application oil Co., Ltd. system etc.
As above-mentioned oil series solvent, can use commercially available product, for example, can enumerate the ア イ ソ パ-シ リ-ズ and the エ Network ソ-Le of エ Network ソ Application chemistry society system; The AF ソ Le ベ Application ト シ リ-ズ of Shin Nihon Oil Co., Ltd's system etc.
As these mineral oil, when considering ink stability etc., the Ppolynuclear aromatic composition as containing 3 yuan of rings or 3 yuan of aromatic hydrocarbonss that condense aromatic ring more than the ring preferably uses less than 3 quality %.In addition, as above-mentioned mineral oil, its mutagen sex index (MI) is lower than 1.0, fragrance (ア ロ マ) composition (%C
A) be 20～55%, aniline point is equal to or less than 100 ℃, and by oily total quality benchmark benzo [a] anthracene, benzo [b] fluoranthene, benzo [j] fluoranthene, benzo [k] fluoranthene, benzo [a] pyrene, dibenzo [a, j] content of Ppolynuclear aromatic such as acridine is equal to or less than 10ppm respectively, and adds up to content to be equal to or less than 50ppm for preferred.
And, aromatic series oil that can also be safe to use (for example, the spy opens flat 11-80640 communique) as required.
As the addition of above-mentioned oil component in emulsified ink for porous printing, have no particular limits, can suitably select preferred 5～80 quality %, more preferably 10～30 quality % according to purpose.
-gelating agent-
Effect as above-mentioned gelating agent is, thereby makes resin gelization contained in the oil phase improve printing ink storage stability, anchorage and flowability etc., preferably with oil phase in resin carry out complex bound compound.As this gelating agent, for example, can enumerate, contain organic acid salt, organic chelate, metallic soap oligopolymer of metals such as Li, Na, K, Al, Ca, Co, Fe, Mn, Mg, Pb, Zn, Zr etc.Particularly, can enumerate organic chelates such as stearate such as metallic naphthenate, Zinic stearas such as sad metal-salt such as aluminium octoate, manganese naphthenate, diisopropoxy list ethyl acetoacetic acid aluminium etc.These can use a kind separately, also can more than 2 kinds or 2 kinds and use.
Addition as above-mentioned gelating agent has no particular limits, and can suitably select according to purpose, with respect to resin total amount in the oil phase, preferably is equal to or less than 15 quality %, more preferably 5～10 quality %.
-pigment extender-
As above-mentioned pigment extender, can add in oil phase, water or the two-phase, so that anti-the spreading and sinking in of printing ink oozed or regulated viscosity, preferably any in inorganic particles and the organic fine particles.As above-mentioned inorganic particles, for example, can enumerate, carclazyte, silicon-dioxide, talcum, clay, lime carbonate, barium sulfate, titanium oxide, aluminum oxide are white, diatomite, potter's clay, mica, aluminium hydroxide etc.As above-mentioned organic fine particles, for example, 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 these multipolymer or the like.
As the addition of above-mentioned pigment extender in emulsified ink for porous printing of the present invention, have no particular limits, can suitably select preferred 0.1～50 quality %, more preferably 1～5 quality % according to purpose.
And, for emulsified ink for porous printing of the present invention, in its oil phase, add wax, roll so that when printing, better printing is separated, or prevent printing with printing drums.In addition, add trolamine or sodium hydroxide etc., the high viscosityization of adding the water-soluble high-molecular compound generation is promoted more toward aqueous phase.Also have, add rust-preventive agent or defoamer, get rusty, or prevent that printing ink from bubbling so that prevent the printing press that when printing, causes because of printing ink toward aqueous phase.As these additives, add aptly as required in can the known material from add emulsified ink for porous printing to, its addition can with the identical degree of dosage of product in the past.
Preparation method as emulsified ink for porous printing of the present invention, have no particular limits, can from known method, suitably select according to purpose, for example, can adopt, modulate oil phase and water liquid in advance respectively by well-established law, water is joined in the above-mentioned oil phase, in known mulser such as dispersion mixer, uniform mixer, high-pressure homogenizer, make it emulsification then and be prepared.Particularly, can be by usual method modulation with triple-roller mill with tinting material, emulsifying agent and the abundant dispersive oil phase of additives such as resin that adds as required, with the aqueous solution of sanitas or mould inhibitor or the water-soluble high-molecular compound that adds as required etc., add wherein and carry out emulsification at leisure to then.
As emulsified ink for porous printing of the present invention, grinding rate 20sec
-1The time the preferred 3～40Pas of viscosity, more preferably 10～30Pas.
As mentioned above, emulsified ink for porous printing of the present invention, place the bad phenomenon of the delay that image occurs in back plug-hole or the printing, and the paper-feed roll can improve two-face printing significantly the time pollutes, therefore be applicable to the porous printing of adopting wheel to change porous printer.
The following describes embodiments of the invention, still, these embodiment do not have any restriction to the present invention.
(embodiment 1)
The preparation of-emulsified ink for porous printing-
Press prescription (quality %) shown in the table 2, (Ha リ マ changes into Co., Ltd.'s system: trade(brand)name P-140) be dissolved in the spindle oil as mineral oil with rosin modified phenolic resin under 150 ℃.Trade(brand)name レ オ De-Le AO-15) and sorbitan monooleate (Kao Corp's system: trade(brand)name レ オ De-Le AO-10), will be as the phthalocyanine blue of tinting material (Japan イ Application Network is made Co., Ltd.'s system), as the Span-83 of tensio-active agent (Kao Corp's system: as the butylated hydroxytoluene of oxidation inhibitor and as the spindle oil of mineral oil, be mixed in the solution of gained, use high speed dispersor, stirred 30 minutes with peripheral speed 10m/sec.Then, use ball mill LMZ2 (ア シ ザ ワ Co., Ltd. system) and carry out dispersion treatment modulation oil phase with following conditions.
＜dispersion condition 〉
Zirconium white system pearl footpath: 1.5mm
Peripheral speed: 12m/sec
Flow velocity: 0.7/min
On the other hand, the Polyvinylpyrolidone (PVP) aqueous solution (BASF society system with 30 quality %, Le PVC テ Star Network K17, the aqueous phase solids component is 2.1 quality %, K value=17) and prepare water in the ion exchanged water as sanitas or mould inhibitor the Para Hydroxy Benzoic Acid methyl esters is dissolved in.
Secondly, use emulsion test machine (ET-3A type, daylight ケ ミ カ Le ズ Co., Ltd. system), packs in this emulsion test machine above-mentioned oil phase liquid on one side that the speed with 400rpm stirs into, Yi Bian slowly add above-mentioned water liquid and carry out emulsification and prepare emulsified ink for porous printing.And when preparation emulsified ink for porous printing 300g, the interpolation of above-mentioned water liquid needs 15 minutes.
(embodiment 2)
The preparation of-emulsified ink for porous printing-
Press prescription (quality %) shown in the table 2, in embodiment 1, except that adding glycerine, prepare emulsified ink for porous printing similarly to Example 1 to above-mentioned aqueous phase.
(embodiment 3)
The preparation of-emulsified ink for porous printing-
Press prescription (quality %) shown in the table 2, remove in above-mentioned oil phase, to add and in addition, prepare emulsified ink for porous printing similarly to Example 1 as the carbon black (コ ロ Application PVC ア Application カ-ボ Application society system, ラ-ベ Application 1080) of tinting material.
(embodiment 4)
The preparation of-emulsified ink for porous printing-
Press prescription (quality %) shown in the table 2, in embodiment 1, except that adding glycerine and sal epsom, prepare emulsified ink for porous printing similarly to Example 1 to above-mentioned aqueous phase.
(embodiment 5)
The preparation of-emulsified ink for porous printing-
Press prescription (quality %) shown in the table 2, in embodiment 1, remove the Polyvinylpyrolidone (PVP) aqueous solution (the BASF society system of using 30 quality % at above-mentioned aqueous phase, Le PVC テ Star Network K30, the aqueous phase solids component is 2.1 quality %, K value=30) in addition, prepare emulsified ink for porous printing similarly to Example 1.
(comparative example 1)
The preparation of-emulsified ink for porous printing-
Press prescription (quality %) shown in the table 3, in embodiment 1, except that the Polyvinylpyrolidone (PVP) aqueous solution that adds 30 quality %, prepare emulsified ink for porous printing similarly to Example 1.
(comparative example 2)
The preparation of-emulsified ink for porous printing-
Press prescription (quality %) shown in the table 3, in embodiment 1, remove the Polyvinylpyrolidone (PVP) aqueous solution (the BASF society system of adding 30 quality %, Le PVC テ Star Network K17, the aqueous phase solids component is 0.8 quality %, K value=17) in addition, prepare emulsified ink for porous printing similarly to Example 1.
(comparative example 3)
The preparation of-emulsified ink for porous printing-
Press prescription (quality %) shown in the table 3, in embodiment 1, remove the Polyvinylpyrolidone (PVP) aqueous solution (the BASF society system of adding 30 quality % at above-mentioned aqueous phase, Le PVC テ Star Network K17, the aqueous phase solids component is 6.8 quality %, K value=17) in addition, prepare emulsified ink for porous printing similarly to Example 1.
(comparative example 4)
The preparation of-emulsified ink for porous printing-
Press prescription (quality %) shown in the table 3, in embodiment 1, remove carbon black (the コ ロ Application PVC ア Application カ-ボ Application society system that in above-mentioned oil phase, adds as tinting material, ラ-ベ Application 1080), and do not add at above-mentioned aqueous phase beyond the Polyvinylpyrolidone (PVP) aqueous solution of 30 quality %, prepare emulsified ink for porous printing similarly to Example 1.
(comparative example 5)
The preparation of-emulsified ink for porous printing-
Press prescription (quality %) shown in the table 3, in embodiment 1, remove the Polyvinylpyrolidone (PVP) aqueous solution (the BASF society system of adding 30 quality % at above-mentioned aqueous phase, Le PVC テ Star Network K60, the aqueous phase solids component is 2.1 quality %, K value=60) and beyond the glycerine, prepare emulsified ink for porous printing similarly to Example 1.
Below, to each emulsified ink for porous printing of embodiment 1～4 and comparative example 1～5, by following operation, the ink stability when plug-hole, the image after the pollution of evaluation paper-feed roll, printing press are placed with rotary drum occurs and high temperature is preserved.The results are shown in table 2 or the table 3.
＜paper-feed roll pollutes 〉
For each emulsified ink for porous printing, (the system リ コ of Co., Ltd.-system, JP5500), the paper-feed roll that takes place when estimating two-face printing pollutes to use porous printer.At first, there is image ground to carry out the 1st 100 printings with the full page of 3 kinds of print speeds (print speed 3 fast In).Place after 10 minutes, do not have plate-making ground at the back side of the 1st printed images with 3 kinds of print speeds and carry out 105 of blank sheet of paper printings, based on the standard of paper-feed roll pollution evaluation shown in the following table 1 the 101st～105 5 are carried out grade evaluation, calculate the grade mean value of 5 images.And the temperature of estimating environment is 20 ℃, and relative humidity is 65%.
Table 1
| Grade | Paper-feed roll pollution evaluation standard |
| 1 | Paper-feed roll on the image pollutes the out of use state of remarkable print. |
| 4 | There is the paper-feed roll on the image to pollute but operable state. |
| 8 | Almost there is not the paper-feed roll on the image to pollute as blank sheet of paper not being applied at the then unconspicuous state in image sample the inside |
| 10 | The state that does not have paper-feed roll to pollute fully. |
Image after rotary drum plug-hole after the＜placement and the placement occurs 〉
Use each emulsified ink for porous printing, with the rotary drum after the printing porous printer (Co., Ltd. system リ コ-system, JP5500) go up place 1 month (ambient temperature and moisture) after, implement to print, by image viewing estimate that rotary drum has or not that plug-hole and image occur number.
Ink stability when＜high temperature is preserved 〉
Each emulsified ink for porous printing 50g is packed in the vial, these vials are preserved 1 month in 60 ℃ thermostatic bath after, observe the condition of surface of each emulsified ink for porous printing etc., by following standard evaluation ink stability.
[judgement criteria]
Zero no separating of oil and water sepn does not flow even turn vial around printing ink yet, and printing ink does not hang from glass bottle opening, and ink stability is excellent.
△: no separating of oil and water sepn, but find that ink viscosity has decline slightly, printing ink was more or less mobile when vial turned around, but ink stability is good.
*: observe separating of oil or water sepn, ink stability is poor.
Table 2
| Composition (quality %) | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | ||
| Oil phase | Phthalocyanine blue | ??3.0 | ??3.0 | ??- | ??3.0 | ??3.0 | |
| Carbon black | ??- | ??- | ??3.0 | ??- | ??- | ||
| Spindle oil | ??15.0 | ??15.0 | ??15.0 | ??15.0 | ??15.0 | ||
| Rosin modified phenolic resin | ??5.0 | ??5.0 | ??5.0 | ??5.0 | ??5.0 | ||
| Span-83 | ??3.7 | ??3.7 | ??3.7 | ??3.7 | ??3.7 | ||
| Sorbitan monooleate | ??2.3 | ??2.3 | ??2.3 | ??2.3 | ??2.3 | ||
| Butylated hydroxytoluene | ??0.1 | ??0.1 | ??0.1 | ??0.1 | ??0.1 | ||
| Water | To the Para Hydroxy Benzoic Acid methyl esters | ??0.1 | ??0.1 | ??0.1 | ??0.1 | ??0.1 | |
| The 30 quality % Polyvinylpyrolidone (PVP) aqueous solution | Addition | ??5.0 | ??5.0 | ??5.0 | ??5.0 | ??5.0 | |
| Solid component concentration | ??2.1 | ??2.1 | ??2.1 | ??2.1 | ??2.1 | ||
| The K value | ??17 | ??17 | ??17 | ??17 | ??30 | ||
| Glycerine | ??- | ??8.0 | ??- | ??8.0 | ??8.0 | ||
| Sal epsom | ??- | ??- | ??- | ??0.7 | ??0.7 | ||
| Ion exchanged water | ??65.8 | ??57.8 | ??65.8 | ??57.1 | ??57.1 | ||
| Add up to (quality %) | ??100.0 | ??100.0 | ??100.0 | ??100.0 | ??100.0 | ||
| Paper-feed roll pollutes | ??9.6 | ??9.6 | ??8.8 | ??9.6 | ??9.6 | ||
| Rotary drum plug-hole after the placement | Do not have | Do not have | Do not have | Do not have | Do not have | ||
| Portrait after the placement occurs | The 5th | The 1st | The 6th | The 1st | The 1st | ||
| Printing ink stability when high temperature is preserved | ??△ | ??△ | ??△ | ??○ | ??○ | ||
Table 3
| Composition (quality %) | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | ||
| Oil phase | Phthalocyanine blue | ??3.0 | ??3.0 | ??3.0 | ??- | ??3.0 | |
| Carbon black | ??- | ??- | ??- | ??3.0 | ??- | ||
| Spindle oil | ??15.0 | ??15.0 | ??15.0 | ??15.0 | ??15.0 | ||
| Rosin modified phenolic resin | ??5.0 | ??5.0 | ??5.0 | ??5.0 | ??5.0 | ||
| Span-83 | ??3.7 | ??3.7 | ??3.7 | ??3.7 | ??3.7 | ||
| Sorbitan monooleate | ??2.3 | ??2.3 | ??2.3 | ??2.3 | ??2.3 | ||
| Butylated hydroxytoluene | ??0.1 | ??0.1 | ??0.1 | ??0.1 | ??0.1 | ||
| Water | To the Para Hydroxy Benzoic Acid methyl esters | ??0.1 | ??0.1 | ??0.1 | ??0.1 | ??0.1 | |
| The 30 quality % Polyvinylpyrolidone (PVP) aqueous solution | Addition | ??- | ??1.9 | ??16.0 | ??- | ??5.0 | |
| Solid component concentration | ??- | ??0.8 | ??6.8 | ??- | ??2.1 | ||
| The K value | ??- | ??17 | ??17 | ??- | ??60 | ||
| Glycerine | ??- | ??- | ??- | ??- | ??8.0 | ||
| Sal epsom | ??- | ??- | ??- | ??- | ??- | ||
| Ion exchanged water | ??70.8 | ??68.9 | ??54.8 | ??70.8 | ??57.8 | ||
| Add up to (quality %) | ??100.0 | ??100.0 | ??100.0 | ??100.0 | ??100.0 | ||
| Paper-feed roll pollutes | ??4.8 | ??4.8 | ??9.6 | ??7.2 | ??9.6 | ||
| Rotary drum plug-hole after the placement | Do not have | Do not have | Take place | Do not have | Take place | ||
| Portrait after the placement occurs | The 5th | The 1st | Because of plug-hole part image does not reset | The 1st | Because of plug-hole part image does not reset | ||
| Printing ink stability when high temperature is preserved | ??× | ??× | ??△ | ??× | ??△ | ||
Can confirm from table 2 and table 3 result, contain the embodiment 1～5 that the K value of counting 1.0～6.0 quality % by solids component with respect to the total mass of above-mentioned water is equal to or less than 30 Polyvinylpyrolidone (PVP), with the comparative example 1 and 4 that does not contain Polyvinylpyrolidone (PVP), the content of Polyvinylpyrolidone (PVP) is pressed the comparative example 2 and 3 of solid component meter less than 1.0～6.0 quality % with respect to the total mass of above-mentioned water, containing the comparative example 5 that the K value surpasses 30 Polyvinylpyrolidone (PVP) compares, the bad phenomenon of the delay that plug-hole after not placing or the image in the printing occur, paper-feed roll when hardly two-face printing taking place pollutes, and the ink stability when high temperature is preserved is also good.
In addition, can also confirm, in embodiment 2 and 4,, improve the image appearance property after placing by adding glycerine at aqueous phase.
Can also confirm in embodiment 4,, when high temperature is preserved, not have the separating of oil and water sepn of printing ink, suppress flowing of printing ink, improve ink stability by adding sal epsom at aqueous phase.
Emulsified ink for porous printing of the present invention, the bad phenomenon of the delay that plug-hole after not placing or the image in the printing occur, paper-feed roll when improving two-face printing significantly pollutes, ink stability excellence when high temperature is preserved, so, be specially adapted to two-face printing applicable to adopting wheel to change the porous printing of porous printer.
Claims (6)
1. emulsified ink for porous printing, it is characterized in that, this printing ink contains oil phase 10～90 quality % and water 90～10 quality %, contain pigment in this oil phase, and this aqueous phase contains the K value of counting 1.0～6.0 quality % by solids component with respect to the total mass of above-mentioned water and is equal to or less than 30 Polyvinylpyrolidone (PVP) as tinting material.
2. the described emulsified ink for porous printing of claim 1, wherein the K value of Polyvinylpyrolidone (PVP) is 15～30.
3. the described emulsified ink for porous printing of claim 1, wherein pigment is phthualocyanine pigment.
4. the described emulsified ink for porous printing of claim 1, wherein aqueous phase contains glycerine.
5. the described emulsified ink for porous printing of claim 4, the content of glycerine wherein is 3.0～15.0 quality % with respect to the total mass of water.
6. the described emulsified ink for porous printing of claim 1, wherein aqueous phase contains sal epsom.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102642415A (en) * | 2012-04-26 | 2012-08-22 | 南京华东电子真空显示科技有限责任公司 | Method for manufacturing internal graduations of oscilloscope tube |
| CN109796795A (en) * | 2019-01-11 | 2019-05-24 | 芜湖市永格节能材料有限公司 | A kind of preparation method of acidproof alkali salt corrosive water antirust paint |
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| JP3246696B2 (en) * | 1994-09-07 | 2002-01-15 | 東北リコー株式会社 | Water-in-oil emulsion ink for stencil printing |
| JPH08218025A (en) * | 1995-02-13 | 1996-08-27 | Riso Kagaku Corp | Emulsion ink for stencil printing plate printing |
| JP4080080B2 (en) * | 1998-04-27 | 2008-04-23 | 東北リコー株式会社 | Water-in-oil emulsion ink for stencil printing |
| JP4080098B2 (en) * | 1998-04-27 | 2008-04-23 | 東北リコー株式会社 | Water-in-oil emulsion ink for stencil printing |
| JP4662585B2 (en) * | 1998-04-27 | 2011-03-30 | 東北リコー株式会社 | Water-in-oil emulsion ink for stencil printing |
| JP4050443B2 (en) * | 1999-09-28 | 2008-02-20 | 東北リコー株式会社 | Water-in-oil emulsion ink for stencil printing |
| JP2002069356A (en) * | 2000-08-29 | 2002-03-08 | Riso Kagaku Corp | Colored emulsion ink for water-in-oil(w/o) type stencil printing |
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| CN102642415A (en) * | 2012-04-26 | 2012-08-22 | 南京华东电子真空显示科技有限责任公司 | Method for manufacturing internal graduations of oscilloscope tube |
| CN109796795A (en) * | 2019-01-11 | 2019-05-24 | 芜湖市永格节能材料有限公司 | A kind of preparation method of acidproof alkali salt corrosive water antirust paint |
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