CN103080246A - Process for manufacturing rosin-modified phenol resin for offset printing ink and process for manufacturing varnish for offset printing ink - Google Patents
Process for manufacturing rosin-modified phenol resin for offset printing ink and process for manufacturing varnish for offset printing ink Download PDFInfo
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- CN103080246A CN103080246A CN2010800688384A CN201080068838A CN103080246A CN 103080246 A CN103080246 A CN 103080246A CN 2010800688384 A CN2010800688384 A CN 2010800688384A CN 201080068838 A CN201080068838 A CN 201080068838A CN 103080246 A CN103080246 A CN 103080246A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
- C09D11/103—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds of aldehydes, e.g. phenol-formaldehyde resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
- C08G8/34—Chemically modified polycondensates by natural resins or resin acids, e.g. rosin
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09D161/14—Modified phenol-aldehyde condensates
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- Engineering & Computer Science (AREA)
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- Health & Medical Sciences (AREA)
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- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention aims to provide a process for manufacturing a rosin-modified phenol resin for offset printing ink suitable for high-speed printing, and a process for manufacturing a varnish for offset printing ink. The technical scheme is that a process for manufacturing a rosin-modified phenol resin for offset printing ink, wherein the rosin-modified phenol resin is a resin that is derived from a rosin, an alkylphenol-aldehyde condensate, and a polyhydric alcohol and has an acid value of 30 or lower and that is characterized both by being manufactured by reacting a rosin with the condensate, and thereafter adding both a polyhydric alcohol in an amount such that the amount of the hydroxyl of the polyhydric alcohol is 0.5 to 0.9 mol relative to one mol of the carboxyl contained in the rosin and a sulfonic acid catalyst to react the rosin, which has reacted with the condensate, with the polyhydric alcohol in the presence of the sulfonic acid catalyst, and by having a metal content of up to 150ppm; and a process for manufacturing a varnish for offset printing ink.
Description
Technical field
The present invention relates to offset printing printing ink rosin modified phenolic resin manufacture method and offset printing printing ink varnish manufacture method.
Background technology
Rosin modified phenolic resin is the resin that rosin based and the reactions such as resol and/or polyvalent alcohol obtain, and excellent because of printing adaptability, as resin for printing ink, especially offset printing is extensively utilized with resin.
In the past, in the offset printing industry, the requirement of Labor-saving, automatization and high speed during to printing was quite high, and its result has had demand to the offset printing technology of stablizing for a long time, can obtain the high quality printing thing under various printing condition.But, along with offset printing speed high speed development, initiation printing-ink gloss difference has appearred, printing adaptability is bad, can not get the problem of high quality printing thing.
Also have, along with the development of offset printing speed high speed, it is dirty easily that forme and print become, so wish to develop to alleviate dirty planographic ink resin.
As the means of improving " dirty " situation, someone has proposed the rosin modified phenolic resin (for example referring to patent documentation 1) of metal ingredient content below 10ppm, do not contain rosin modified phenolic resin with having proposed to adopt, and contain the method for the lithography ink component (for example referring to patent documentation 2) of alpha-olefinic polymer.The printing-ink of also using as offset printing, the rosin modified phenolic resin of the specified molecular weight that has proposed to allow rosin based, the soluble phenolic resin that consists of with the phenol of the alkyl with carbon number 10～20 and polyvalent alcohol carry out reacting by heating in the presence of acid catalyst and obtained namely carries out specific and Abietyl modified phenolic aldehyde (referring to patent documentation 3) that obtain to the solvability of this resin.Yet, also extremely do not adapt to the print speed high speed by the resulting used for offset ink resin of these means.So, see with regard to present situation, wish to develop and keep the resin for printing ink that the solvability of solvent is suitable for high speed printing.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2008-274150 communique
Patent documentation 2: TOHKEMY 2005-290084 communique
Patent documentation 3: Japan's special permission No. 3298268 communique (Unexamined Patent 7-126338 communique)
Summary of the invention
Technical problem
The object of the invention just is to solve the problem points of prior art, and a kind of offset printing printing ink rosin modified phenolic resin manufacture method and offset printing printing ink varnish manufacture method that is suitable for high speed printing is provided.
Solution
Present inventors etc. are through with keen determination research, and it found that the manufacture method of the rosin modified phenolic resin that is suitable for obtaining being suitable for the dirty few flexographic ink of offset printing speed high speed, forme and print, so reach the present invention.
That is, as follows for the technical scheme that realizes the object of the invention:
(1) a kind of offset printing printing ink rosin modified phenolic resin manufacture method, this resin be from the polycondensate of rosin based, alkylphenol and aldehyde and polyol derivative, the rosin modified phenolic resin of acid value below 30; Make after the reaction of rosin based and above-mentioned polycondensate, add polyvalent alcohol, and 1 mole of the contained carboxyl of the relative rosin based of amount of hydroxyl groups that makes addition satisfy polyvalent alcohol is more than 0.5 mole below 0.9 mole; And the interpolation sulfonic acid catalyst makes with the reacted rosin based of above-mentioned polycondensate and polyvalent alcohol and reacts in the presence of sulfonic acid catalyst; The metal maximum level is 150ppm.
(2) by the manufacture method of above-mentioned (1) described offset printing printing ink with rosin modified phenolic resin, it is characterized in that the catalyzer that above-mentioned metal uses when making above-mentioned polycondensate.
(3) a kind of offset printing printing ink varnish manufacture method, at least being dissolved in plant oil and/or printing ink solvent with the resulting offset printing printing ink of rosin modified phenolic resin manufacture method with rosin modified phenolic resin according to above-mentioned (1) or (2) described offset printing printing ink, in the LITHOTRONIC emulsion test, maximum emulsification rate and moment of torsion rate of rise long-pending be more than 1.0 below 4.0.
The effect of invention
According to the present invention, can provide rosin modified phenolic resin manufacture method, the offset printing printing ink varnish manufacture method of the dirty few offset printing printing ink of a kind of high speed, forme and print that can obtain being suitable for offset printing speed.
Embodiment
The present invention is a kind of offset printing printing ink rosin modified phenolic resin manufacture method, this resin be from the polycondensate of rosin based, alkylphenol and aldehyde and polyol derivative, the rosin modified phenolic resin of acid value below 30; Make after the polycondensate reaction of rosin based and alkylphenol and aldehyde, add polyvalent alcohol and sulfonic acid catalyst, 1 mole of the contained carboxyl of the relative rosin based of amount of hydroxyl groups that the addition of polyvalent alcohol satisfies polyvalent alcohol is more than 0.5 mole below 0.9 mole, accordingly, the esterification of the hydroxyl in the existing carboxyl and polyvalent alcohol in the reacted rosin based of polycondensate of rosin based and alkylphenol and aldehyde is carried out in the presence of sulfonic acid catalyst, make thus offset printing printing ink rosin modified phenolic resin.
Offset printing printing ink rosin modified phenolic resin of the present invention is that the polycondensate with rosin based, alkylphenol and aldehyde (is made " polycondensate " with the polycondensate abbreviation of alkylphenol and aldehyde among the present invention sometimes.) and the resin of polyvalent alcohol for must raw material obtaining.
Above-mentioned rosin based refers to rosin and rosin derivative.Rosin is natural resin, and gum resin, starex (tall oil rosin) and wood rosin etc. are known as rosin.The acid value of gum resin and starex is more than 165 below 170, and the acid value of wood rosin is 160～170, so gum resin, starex and wood rosin have common acid value.Can list the rosin derivatives such as staybelite, polymerized rosin and nilox resin.Also have, rosin derivative also comprises as required to the above-mentioned modified rosin that those have carried out modification with α, beta-unsaturated carboxylic acid classes such as maleic anhydride, fumaric acid, vinylformic acid.
Above-mentioned staybelite can be by hydrogenation makes part or all saturated obtaining of unsaturated link(age) to rosin.
Above-mentioned polymerized rosin is can be by with rosin rosin of obtaining of polymerization in addition in the presence of the catalyzer such as sulfuric acid, is also to comprise monomer, polymeric mixture more than the tripolymer except comprising dimer.
Nilox resin can obtain like this: make hydrogen in intermolecular movement by rosin being heated etc., the unsaturated link(age) that makes the one party molecule is saturated and make simultaneously unsaturatedization of saturated bond of the opposing party's molecule.
Abovementioned alkyl phenol can use cresols, amyl phenol, dihydroxyphenyl propane, p-butylphenol (para-butylphenol), paraoctyl phenol (para-octylphenol), p-nonylphenol (para-nonylphenol), to 4-dodecylphenol (para-dodecylphenol), dibutyl phenol (dibutylphenol), xylenol (dimethylphenol) etc.These both can use separately also and can and use.From the viewpoint of market value, acquisition easiness, used for offset ink resin property, especially preferred p-butylphenol, paraoctyl phenol, p-nonylphenol.
Above-mentioned aldehyde can use formaldehyde, Paraformaldehyde 96 (formaldehyde, acetaldehyde (acetaldehyde), the propionic aldehyde (propionaldehyde) etc. such as paraformaldehyde), trioxane (trioxane).This is wherein also from viewpoints such as reactivities, especially preferred formaldehyde, Paraformaldehyde 96.Alkylphenol is preferred with the ratio of aldehyde: 1 mole of relative alkylphenol, aldehyde are more than 1.7 moles below 2.3 moles.If in above-mentioned scope, then as easy to the processing of rosin modified phenolic resin.
Above-mentioned polycondensate can use and for example make alkylphenol and aldehyde in advance reaction and the common thermosetting phenolic (Resol) that produces and/or make alkylphenol and aldehyde further makes alkylphenol and aldehyde react after reacting in advance and the Novolac-Resol that produces again in the presence of an acidic catalyst in the presence of basic catalyst in the presence of basic catalyst.These both can use separately also and can and use.
Can list as above-mentioned basic catalyst: the alkanolamines such as the alkylamines such as metal catalyst class, ammonia, methylamine, dimethylamine, diethylamine, Trimethylamine 99, ethamine, diethylamine, triethylamine, thanomin, diethanolamine, trolamine such as sodium hydroxide, potassium hydroxide, calcium oxide, calcium hydroxide, zinc oxide etc.Also have, as above-mentioned an acidic catalyst, can list: sulfonate or the mineral acids such as sulfuric acid, hydrochloric acid such as p-methyl benzenesulfonic acid, Witco 1298 Soft Acid, methylsulphonic acid, ethylsulfonic acid.The usage quantity of catalyzer is preferred: polycondensate 100 weight parts are below above 2.5 weight parts of 0.01 weight part relatively.When the usage quantity of catalyzer is less than 0.01 weight part, can not get polycondensate, and when surpassing 2.5 weight part, then be difficult to obtain the few rosin modified phenolic resin of metal content.
Offset printing printing ink of the present invention is with in the rosin modified phenolic resin manufacture method, be preferably more than the 20 quality % below the 65 quality % with respect to the above-mentioned polycondensate usage rate of rosin based, polycondensate and polyvalent alcohol total amount, especially be preferably below the above 50 quality % of 25 quality %.If less than 20 quality %, then often offset printing printing ink causes when viscosity deficiency or printing to fly China ink (misting) with the molecular weight step-down of rosin modified phenolic resin.And when surpassing 65 quality %, often offset printing printing ink significantly rises with the affinity of rosin modified phenolic resin and solvent, and drying became slow during printing.
Can list ethylene glycol as above-mentioned polyvalent alcohol, Diethylene Glycol, triethylene glycol, polyoxyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, butyleneglycol, hexylene glycol, ethohexadiol, nonanediol, the dibasic alcohol such as neopentyl glycol, trivalent alcohol, Glycerol dimer, trimethylolethane, TriMethylolPropane(TMP), ditrimethylolpropane (ditrimethylolpropane), tetramethylolmethane (pentaerythritol), Dipentaerythritol, the alcohols that 3 valencys such as sorbyl alcohol are above etc.These both can use separately also and can and use.This wherein, from the suitable adjustment offset printing printing ink purpose with the molecular weight of rosin modified phenolic resin, fusing point etc., preferred trivalent alcohol and/or tetramethylolmethane.The usage quantity of polyvalent alcohol is to be the amount in this scope below 0.9 mole more than 0.5 mole in the relative amount of hydroxyl groups of 1 mole of polyvalent alcohol of carboxyl of the rosin based of using.
By being made as this scope, just becoming the offset printing printing ink rosin modified phenolic resin that is suitable for offset printing printing ink.
Can list sulfonate and the sulfuric acid such as p-methyl benzenesulfonic acid, Witco 1298 Soft Acid (dodecyl benzenesulfonic acid), methylsulphonic acid, ethylsulfonic acid as the used sulfonic acid catalyst of esterification.The usage quantity of sulfonic acid catalyst is preferred: rosin based and polyvalent alcohol summation 100 weight parts are below above 0.40 weight part of 0.20 weight part relatively.
Offset printing printing ink of the present invention is preferably below 30 with the acid value of rosin modified phenolic resin, more preferably below 23 more than 1.If this is because acid value is 30 with next the cause that when printing be difficult for occuring the tendency of the problem such as dirty to be arranged.
Offset printing printing ink of the present invention is not particularly limited with the fusing point of rosin modified phenolic resin, but is preferably more than 130 ℃ below 200 ℃.If this is because 130 ℃ of less thaies drying property and solidify the cause of remarkable variation then.
Offset printing printing ink is preferably more than 10,000 below 100,000 with the molecular weight of rosin modified phenolic resin among the present invention.This is because the cause that varnish viscosity is suitable for using under above-mentioned scope.
Also have, better offset printing printing ink rosin modified phenolic resin among the present invention, the value of heptane maximum permission quantity (heptane tolerance level) is more than the 10mL/g.In addition, heptane maximum permission quantity value is the index of the intermiscibility of expression resin and petroleum-type solvent and/or vegetables oil, and the higher expression intermiscibility of heptane maximum permission quantity numerical value is higher.Among the present invention, the heptane maximum permission quantity refers to: when dripping normal heptane toward 33.3% toluene solution of rosin modified phenolic resin gonorrhoea normal heptane amount (mL) with the amount of resin (g) that is dissolved in toluene except and the value that obtains.Here so-called gonorrhoea refers to: concentration whatever also can not show deliquescent state at all.
Offset printing printing ink of the present invention with rosin modified phenolic resin not containing metal be preferred, even if contain metal, this metal maximum level also only is 150ppm.When offset printing printing ink used the amount of the contained metal of rosin modified phenolic resin to surpass 150ppm, often resistance to emulsion worsened or gonorrhoea.Be not that to do one's utmost to reduce metal content better, since offset printing printing ink with rosin modified phenolic resin metallic content be the metal of making the catalyzer of time use from polycondensate, fully remove metal and can cause polycondensate manufacturing cost this result that rises.Especially during not enough 3ppm, can be because of the problem in the manufacturing process so that cost uprise.
Offset printing printing ink varnish among the present invention contains offset printing printing ink with rosin modified phenolic resin and at least plant oil and/or printing ink solvent, as required, can also contain to be useful on and give elastic jelling agent, can also contain in addition the additives such as antioxidant.
With the used plant oil of varnish, can use various known product as offset printing printing ink, and indefinite.For example can list Semen Lini oil, tung oil, safflower oil, synourin oil, soybean wet goods vegetables oil, also have in addition the monoesters of the above-mentioned vegetables oil such as Semen Lini oil fatty acid methyl ester (fatty acid methyl ester), methyl soyate, Semen Lini oil fatty-acid ethyl ester, ethyl ester of soybean oil, Semen Lini oil lipid acid propyl ester, soya fatty acid propyl ester, Semen Lini oil fatty acid butyl ester, soya fatty acid butyl ester etc.These both can use separately also can be suitably also with two or more.In the middle of these, from the angle of print drying property, have the vegetables oil of unsaturated link(age) in the preferred molecule, from reducing the angle of environmental pressure, especially preferred soybean oil.
With the used printing ink solvent of varnish, can use in the past known printing ink solvent as offset printing printing ink, and indefinite.For example can list the petroleum-type solvent of Shin Nihon Oil Co., Ltd's system: No. 0 Solvent, No. 4 Solvent, No. 5 Solvent, No. 6 Solvent, No. 7 Solvent, AF Solvent4 number, AF Solvent5 number, AF Solvent6 number, AF Solvent7 number etc.These both can use separately also can be suitably also with two or more.Especially consider from the environmental cure aspect, use preferably that about 200 ℃ of boiling points are above, the aromatic hydrocarbon containing ratio is AF Solvent following about 1 % by weight.In addition, when the needs use alleviates the printing-ink of environmental pressure, do not use printing ink only to use plant oil to get final product with solvent.
As the offset printing printing ink used jelling agent of varnish; can use for example aluminium octoate (aluminum octanoate); aluminum stearate (aluminum stearate); aluminum isopropylate (aluminium triisopropoxide); aluminium butoxide (aluminum tributoxide); two propyl alcohol monoacylphosphine aluminum acetates (aluminum dipropoxide monoacetyl acetate); dibutoxy monoacylphosphine aluminum acetate (aluminum dibutoxide monoacetyl acetate); triacetyl aluminum acetate (aluminum triacetyl acetate); titanium tetraisopropylate (titanium tetraisopropoxide); four titanium butoxide (tetrabutoxy titanium); dipropoxy bis-acetylacetonate titanium (dipropoxybis (acetylacetonato) titanium); tetrabutyl zirconate (tetrabutoxy zirconium); toluene-2,4-diisocyanate (tolylene diisocyanate); two isocyanic acid diphenyl esters (diphenyl diisocyanate); hexamethylene diisocyanate (hexamethylene diisocyanate); eylylene diisocyanate (xylylene diisocyanate); the known product such as isophorone diisocyanate (isophorone diisocyanate) are not particularly limited.These both can use separately also can mix two or more uses.
, can use such as the various known product such as 2,6 ditertiary butyl p cresol with varnish used antioxidant as offset printing printing ink, be not particularly limited.
Offset printing printing ink with varnish can by mix and blend above-mentioned each become to assign to make, but when mix and blend, the heating of the temperature in the scope below 240 ℃ more than 100 ℃ mixes each composition dissolving usually, uses additive as required and obtains.
Offset printing printing ink is used below the above 60 quality % of the preferred 30 quality % of ratio of rosin modified phenolic resin, below the above 50 quality % of especially preferred 35 quality % with the offset printing printing ink in the varnish.This is because the cause that varnish viscosity becomes and is suitable for using under above-mentioned scope.
Offset printing printing ink is measured by following condition with the LITHOTRONIC emulsify at a high speed tester of the LITHOTRONIC emulsion test employing NOVOCONTROL company system of varnish among the present invention.
Treatment time (the in advance churning time that does not add water) 300sec
Stirring velocity 1200rpm
The amount 25g of sample (varnish)
40 ℃ of temperature
Amount 2mL/ divides under the water droplet
10 ° of stirring rake (propeller) stirring rake angles, thickness 1.5mm
Stirring rake and sample cup for liquid bottom surface apart from 1mm
When under the water droplet, allow water injection needle contact the sample cup for liquid wall, make water enter printing ink quietly, the torque curve noise suppression that water droplet is caused arrives minimum.
Maximum emulsification rate and moment of torsion rate of rise are as follows.
Maximum emulsification rate (EC (Emulsification Capacity: the % of unit).Below sometimes be called for short EC.) calculate in order to following formula.
In addition, in the calculating, maximum emulsification rate is defined as when moment of torsion and begins change and unstable, and the standard deviation of the nearest 10 times test value of torque value surpasses 100 o'clock EC value.
EC (%)=(amount of dripping of water)/(sample size) * 100
The moment of torsion rate of rise calculates with following formula.
Moment of torsion rate of rise (%)=(T max-T min)/T min * 100
Wherein, T min is minimal torque, and T max is maximum torque, is defined as follows.
While stirring the water that drips, initial moment of torsion reduces, and the minimal torque value is shown in the sample varnish of packing into toward sample cup for liquid.Thereafter, along with the amount of the dripping increase of water, torque value increases, and maximum torque is shown.When continuing to drip again, a part of water separates from sample, and it is unstable that moment of torsion sharply reduces or torque curve becomes.
Long-pending being preferably 1.0 or more below 4.0 of the maximum emulsification rate that calculates as described above and moment of torsion rate of rise, this be because do not cause initial stage emulsification bad with Over emulsfication problem and reach the cause of suitable resistance to emulsion.
Offset printing printing ink contain above-mentioned offset printing printing ink with rosin modified phenolic resin and/or above-mentioned offset printing printing ink with varnish, pigment, vegetables oil and/or solvent, also can contain as required the used for offset ink additive, for example be used for improving tensio-active agent, wax, dry promotor (dryer), the drying retarder of ink flow or ink pellet surface tunicle.
The contained pigment of offset printing printing ink can list the painted pigment such as yellow, redness, blue look or ?look.The pigment containing ratio is preferably below the above 30 quality % of 3 quality %.
The used vegetables oil of offset printing printing ink can use various known, and indefinite.For example Semen Lini oil, tung oil, safflower oil, synourin oil, soybean wet goods vegetables oil can be listed, the monoesters of the above-mentioned vegetables oil such as Semen Lini oil fatty acid methyl ester, methyl soyate, Semen Lini oil fatty-acid ethyl ester, ethyl ester of soybean oil, Semen Lini oil lipid acid propyl ester, soya fatty acid propyl ester, Semen Lini oil fatty acid butyl ester, soya fatty acid butyl ester etc. can be listed in addition.These both can use separately also can be suitably also with two or more.
The solvent that offset printing printing ink is used can use existing known printing ink solvent, is not particularly limited.For example can list the petroleum-type solvent of Shin Nihon Oil Co., Ltd's system, i.e. No. 0 Solvent, No. 4 Solvent, No. 5 Solvent, No. 6 Solvent, No. 7 Solvent, AF Solvent4 number, AF Solvent5 number, AF Solvent6 number, AF Solvent7 number etc.These both can use separately also can be suitably also with two or more.Especially from the environmental cure aspect, use preferably that about 200 ℃ of boiling points are above, following AF Solvent about aromatic hydrocarbon containing ratio 1 % by weight.In addition, in the occasion that requires to use the printing-ink that alleviates environmental pressure, without the printing ink solvent, only get final product with plant oil.The preferred solvent containing ratio is 5～50 quality %.
When not using offset printing printing ink of the present invention to use varnish, the used offset printing printing ink of offset printing printing ink is preferably more than the 10 quality % below the 50 quality %, more preferably below the above 40 quality % of 15 quality % with the containing ratio of rosin modified phenolic resin in offset printing printing ink.If less than 10 quality %, it is inadequate the offset printing ink viscosity then can to occur, and simultaneously, colo(u)rant dispersion can not stabilization and the problem of condensing.And if above 50 quality %, then the offset printing ink viscosity often becomes too high.
Even if in the occasion of modulating offset printing printing ink with offset printing printing ink of the present invention with varnish and offset printing printing ink with rosin modified phenolic resin, offset printing printing ink in the offset printing printing ink also is preferably below the above 50 quality % of 10 quality % with the containing ratio of rosin modified phenolic resin, more preferably below the above 40 quality % of 15 quality %.
Containing ratio in the offset printing printing ink of the plant oil that offset printing printing ink is used and/or solvent is the whole amounts except other all the components.The usage rate of plant oil and solvent can change according to purpose.For example not contain solvent as the occasion of the Non-VOC type printing ink of speciality, do not contain solvent, only use plant oil.For example in the occasion of the offset rotary printing that carries out warm air drying with printing ink, reduce the usage quantity of plant oil, use solvent more.Come in, as the corresponding type printing ink of environment, the Soybean Oil Ink start to excel, turning offset printing at wheel also has many soybean wet goods that contain in printing ink.
Can use the salt of the carboxylic acids such as the metals such as cobalt, manganese, lead, iron, zinc and caprylic acid, naphthoic acid, neodecanoic acid as the used dry promotor (dryer) of offset printing printing ink, i.e. metallic soaps class etc.
Can use Resorcinol (hydroquinone), methoquinone, Tert. Butyl Hydroquinone (tert-butyl hydroquinone) etc. as drying retarder.
The offset printing printing ink additive that offset printing printing ink is used, as long as can be mixed in equably offset printing printing ink, which procedure interpolation all can in offset printing printing ink is made.Both can add also and can add in the stage that offset printing printing ink is made with varnish in advance in the final stage that offset printing printing ink is made.Also have, also can make an addition to first employed other resin, it is made offset printing printing ink use with varnish.
Offset printing printing ink can by roll with known printing ink manufacturing installations such as roller mill (roll mill), ball mill (ball mill), masher (attritor), sand mills (sand mill) China ink, the modulation obtain.
Embodiment
The below more specifically describes the present invention according to embodiment, but the present invention is limited by these embodiment.In addition, in the example, section, % be representation quality part, quality % respectively.
Embodiment 1
(Production Example 1: the manufacturing of polycondensate F-1)
In the four-hole boiling flask of having installed agitator, reflux condensing tube and thermometer, drop into 1500 parts of 2200 parts of p-nonyl phenols (p-nonylphenol), 652 parts of 92% Paraformaldehyde 96s and toluene (toluene), after the four-hole boiling flask content has been heated to 50 ℃, under this temperature, in four-hole boiling flask, dropped into 30 parts in 48% sodium hydroxide.The four-hole boiling flask content was heated to 80 ℃ of reactions after 6 hours, with in 40 parts of 35% hydrochloric acid with the four-hole boiling flask content, wash with 500 parts of water.After leaving standstill 6 hours, remove water layer, drop into again 500 parts in water and wash.After leaving standstill 6 hours, remove water layer, obtained thus polycondensate F-1.
(manufacturing of rosin modified phenolic resin 1 of offset printing printing ink)
Toward having installed agitator, having dropped into 800 parts of gum resin with the reflux exchanger of water separator and the removable flask of four-hole (separable flask) of thermometer, be heated to 170 ℃ while passing into nitrogen, above-mentioned gum resin is dissolved, 800 parts of polycondensate F-1 that make in Production Example 1 have been dropped into while stirring the gum resin that has become the state that dissolves toward this gum resin, heat up again after dropping into, until 215 ℃, under this temperature, drop into 40 parts of 20 parts of trivalent alcohols and tetramethylolmethanes, be warmed up to again 250 ℃ after the input.In addition, the total usage quantity of trivalent alcohol and tetramethylolmethane is: 1 mole of the relative carboxyl that has used gum resin, the amount of hydroxyl groups in trivalent alcohol and the tetramethylolmethane is equivalent to 0.77 mole.In the intensification, with the reflux exchanger with water separator toluene and water are discharged outside the reaction system, make reaction 4 hours at the state that is maintained at 250 ℃, the removable flask contents of four-hole is taked out a part, when acid value becomes 50mgKOH/g, 2 parts of p-methyl benzenesulfonic acids have been put in the removable flask of four-hole, then 250 ℃ of reactions 5 hours, keep 250 ℃ constant, reduced pressure in 60 minutes to carrying out in the four-hole boiling flask with 20mmHg with drawdown pump, produced thus offset printing printing ink rosin modified phenolic resin 1.150 ℃ of the fusing points of gained offset printing printing ink usefulness rosin modified phenolic resin 1, acid value 20mgKOH/g, heptane maximum permission quantity 21mL/g, weight-average molecular weight 80,000 is from the metal content 23ppm of catalyzer.
Embodiment 2
(Production Example 2: the manufacturing of polycondensate F-2)
In the four-hole boiling flask of having installed agitator, reflux condensing tube and thermometer, drop into 1500 parts of 1200 parts of p-tert-butylphenols, 412 parts of paraoctyl phenols, 652 parts of 92% Paraformaldehyde 96s and toluene, after the four-hole boiling flask content has been heated to 50 ℃, under this temperature, in four-hole boiling flask, dropped into 50 parts in 48% sodium hydroxide.The four-hole boiling flask content was heated to 80 ℃ of reactions after 6 hours, with in 40 parts of 35% hydrochloric acid with the four-hole boiling flask content, wash with 500 parts of water.After leaving standstill 6 hours, remove water layer, drop into again 500 parts in water and wash.After leaving standstill 6 hours, remove water layer, obtained thus polycondensate F-2.
(manufacturing of rosin modified phenolic resin 2 of offset printing printing ink)
Toward having installed agitator, having dropped into 800 parts of gum resin with the reflux exchanger of water separator and the removable flask of four-hole of thermometer, be heated to 170 ℃ while passing into nitrogen, above-mentioned gum resin is dissolved, 570 parts of polycondensate F-2 that make in Production Example 2 have been dropped into while stirring the gum resin that has become the state that dissolves toward this gum resin, heat up again after dropping into, until 215 ℃, under this temperature, drop into 55 parts of 10 parts of trivalent alcohols and tetramethylolmethanes, be warmed up to again 250 ℃ after the input.In addition, the total usage quantity of trivalent alcohol and tetramethylolmethane is: 1 mole of the relative carboxyl that has used gum resin, the amount of hydroxyl groups in trivalent alcohol and the tetramethylolmethane is equivalent to 0.82 mole.In the intensification, with the reflux exchanger with water separator toluene and water are discharged outside the reaction system, make reaction 4 hours at the state that is maintained at 250 ℃, the removable flask contents of four-hole is taked out a part, when acid value becomes 50mgKOH/g, 2 parts of p-methyl benzenesulfonic acids have been put in the removable flask of four-hole, then 250 ℃ of reactions 5 hours, keep 250 ℃ constant, reduced pressure in 60 minutes to carrying out in the four-hole boiling flask with 20mmHg with drawdown pump, produced thus offset printing printing ink rosin modified phenolic resin 2.180 ℃ of the fusing points of gained offset printing printing ink usefulness rosin modified phenolic resin 2, acid value 18mgKOH/g, heptane maximum permission quantity 15mL/g, weight-average molecular weight 1.3 ten thousand is from the metal content 12ppm of catalyzer.
Embodiment 3
(Production Example 3: the manufacturing of polycondensate F-3)
In the four-hole boiling flask of having installed agitator, reflux condensing tube and thermometer, drop into 1500 parts of 2060 parts of octyl phenols, 652 parts of 92% Paraformaldehyde 96s and toluene, after the four-hole boiling flask content has been heated to 50 ℃, under this temperature, in four-hole boiling flask, dropped into 50 parts in 48% sodium hydroxide.The four-hole boiling flask content was heated to 80 ℃ of reactions after 6 hours, with in 40 parts of 35% hydrochloric acid with the four-hole boiling flask content, wash with 500 parts of water.After leaving standstill 6 hours, remove water layer, drop into again 500 parts in water and wash.After leaving standstill 6 hours, remove water layer, obtained thus polycondensate F-3.
(manufacturing of rosin modified phenolic resin 3 of offset printing printing ink)
Toward having installed agitator, having dropped into 800 parts of gum resin with the reflux exchanger of water separator and the removable flask of four-hole of thermometer, be heated to 170 ℃ while passing into nitrogen, above-mentioned gum resin is dissolved, 650 parts of polycondensate F-3 that make in Production Example 3 have been dropped into while stirring the gum resin that has become the state that dissolves toward this gum resin, heat up again after dropping into, until 215 ℃, under this temperature, drop into 65 parts of trivalent alcohols, be warmed up to again 250 ℃ after the input.In addition, the trivalent alcohol usage quantity is: relatively used 1 mole of the carboxyl of gum resin, the amount of hydroxyl groups in the trivalent alcohol is equivalent to 0.89 mole.In the intensification, with the reflux exchanger with water separator toluene and water are discharged outside the reaction system, make reaction 4 hours at the state that is maintained at 250 ℃, the removable flask contents of four-hole is taked out a part, when acid value becomes 50mgKOH/g, 2 parts of p-methyl benzenesulfonic acids have been put in the removable flask of four-hole, then 250 ℃ of reactions 5 hours, keep 250 ℃ constant, reduced pressure in 60 minutes to carrying out in the four-hole boiling flask with 20mmHg with drawdown pump, produced thus offset printing printing ink rosin modified phenolic resin 3.160 ℃ of the fusing points of gained offset printing printing ink usefulness rosin modified phenolic resin 3, acid value 19mgKOH/g, heptane maximum permission quantity 17mL/g, weight-average molecular weight 20,000 is from the metal content 10ppm of catalyzer.
Embodiment 4
(Production Example 4: the manufacturing of polycondensate F-4)
In the four-hole boiling flask of having installed agitator, reflux condensing tube and thermometer, drop into 1500 parts of 1500 parts of p-tert-butylphenols, 652 parts of 92% Paraformaldehyde 96s and toluene, after the four-hole boiling flask content has been heated to 50 ℃, under this temperature, in four-hole boiling flask, dropped into 50 parts in 48% sodium hydroxide.The four-hole boiling flask content was heated to 80 ℃ of reactions after 6 hours, with in 40 parts of 35% hydrochloric acid with the four-hole boiling flask content, wash with 500 parts of water.After leaving standstill 6 hours, remove water layer, drop into again 500 parts in water and wash.After leaving standstill 6 hours, remove water layer, obtained thus polycondensate F-4.
(manufacturing of rosin modified phenolic resin 4 of offset printing printing ink)
Toward having installed agitator, having dropped into 800 parts of gum resin with the reflux exchanger of water separator and the removable flask of four-hole of thermometer, be heated to 170 ℃ while passing into nitrogen, above-mentioned gum resin is dissolved, 570 parts of polycondensate F-4 that make in Production Example 4 have been dropped into while stirring the gum resin that has become the state that dissolves toward this gum resin, heat up again after dropping into, until 215 ℃, under this temperature, drop into 55 parts of 10 parts of trivalent alcohols and tetramethylolmethanes, be warmed up to again 250 ℃ after the input.In addition, the total usage quantity of trivalent alcohol and tetramethylolmethane is: 1 mole of the relative carboxyl that has used gum resin, the amount of hydroxyl groups in trivalent alcohol and the tetramethylolmethane is equivalent to 0.82 mole.In the intensification, with the reflux exchanger with water separator toluene and water are discharged outside the reaction system, make reaction 4 hours at the state that is maintained at 250 ℃, the removable flask contents of four-hole is taked out a part, when acid value becomes 50mgKOH/g, 2 parts of p-methyl benzenesulfonic acids have been put in the removable flask of four-hole, then 250 ℃ of reactions 5 hours, keep 250 ℃ constant, reduced pressure in 60 minutes to carrying out in the four-hole boiling flask with 20mmHg with drawdown pump, produced thus offset printing printing ink rosin modified phenolic resin 4.185 ℃ of the fusing points of gained offset printing printing ink usefulness rosin modified phenolic resin 4, acid value 21mgKOH/g, heptane maximum permission quantity 13mL/g, weight-average molecular weight 20,000 is from the metal content 10ppm of catalyzer.
Embodiment 5
(manufacturing of rosin modified phenolic resin 5 of offset printing printing ink)
Toward having installed agitator, having dropped into 800 parts of gum resin with the reflux exchanger of water separator and the removable flask of four-hole of thermometer, be heated to 170 ℃ while passing into nitrogen, above-mentioned gum resin is dissolved, 870 parts of polycondensate F-3 that make in Production Example 3 have been dropped into while stirring the gum resin that has become the state that dissolves toward this gum resin, heat up again after dropping into, until 215 ℃, under this temperature, drop into 40 parts of 10 parts of trivalent alcohols and tetramethylolmethanes, be warmed up to again 250 ℃ after the input.In addition, the total usage quantity of trivalent alcohol and tetramethylolmethane is: 1 mole of the relative carboxyl that has used gum resin, the amount of hydroxyl groups in trivalent alcohol and the tetramethylolmethane is equivalent to 0.64 mole.In the intensification, with the reflux exchanger with water separator toluene and water are discharged outside the reaction system, make reaction 4 hours at the state that is maintained at 250 ℃, the removable flask contents of four-hole is taked out a part, when acid value becomes 50mgKOH/g, 2 parts of p-methyl benzenesulfonic acids have been put in the removable flask of four-hole, then 250 ℃ of reactions 5 hours, keep 250 ℃ constant, reduced pressure in 10 minutes to carrying out in the four-hole boiling flask with 20mmHg with drawdown pump, produced thus offset printing printing ink rosin modified phenolic resin 5.175 ℃ of the fusing points of gained offset printing printing ink usefulness rosin modified phenolic resin 5, acid value 20mgKOH/g, heptane maximum permission quantity 16mL/g, weight-average molecular weight 100,000 is from the metal content 16ppm of catalyzer.
Embodiment 6
(manufacturing of rosin modified phenolic resin 6 of offset printing printing ink)
Toward having installed agitator, having dropped into 800 parts of gum resin with the reflux exchanger of water separator and the removable flask of four-hole of thermometer, be heated to 170 ℃ while passing into nitrogen, above-mentioned gum resin is dissolved, 500 parts of polycondensate F-2 that make in Production Example 2 have been dropped into while stirring the gum resin that has become the state that dissolves toward this gum resin, heat up again after dropping into, until 215 ℃, under this temperature, drop into 40 parts of 20 parts of trivalent alcohols and tetramethylolmethanes, be warmed up to again 250 ℃ after the input.In addition, the total usage quantity of trivalent alcohol and tetramethylolmethane is: 1 mole of the relative carboxyl that has used gum resin, the amount of hydroxyl groups in trivalent alcohol and the tetramethylolmethane is equivalent to 0.77 mole.In the intensification, with the reflux exchanger with water separator toluene and water are discharged outside the reaction system, make reaction 4 hours at the state that is maintained at 250 ℃, the removable flask contents of four-hole is taked out a part, when acid value becomes 50mgKOH/g, 2 parts of Witco 1298 Soft Acids have been put in the removable flask of four-hole, then 250 ℃ of reactions 5 hours, keep 250 ℃ constant, reduced pressure in 60 minutes to carrying out in the four-hole boiling flask with 20mmHg with drawdown pump, produced thus offset printing printing ink rosin modified phenolic resin 6.174 ℃ of the fusing points of gained offset printing printing ink usefulness rosin modified phenolic resin 6, acid value 21mgKOH/g, heptane maximum permission quantity 20mL/g, weight-average molecular weight 2.8 ten thousand is from the metal content 20ppm of catalyzer.
Comparative example 1
(manufacturing of rosin modified phenolic resin C1 of offset printing printing ink)
Toward having installed agitator, having dropped into 800 parts of gum resin with the reflux exchanger of water separator and the removable flask of four-hole of thermometer, be heated to 170 ℃ while passing into nitrogen, above-mentioned gum resin is dissolved, 650 parts of polycondensate F-3 that make in Production Example 3 have been dropped into while stirring the gum resin that has become the state that dissolves toward this gum resin, heat up again after dropping into, until 215 ℃, under this temperature, drop into 1 part in 65 parts of trivalent alcohols and zinc oxide, be warmed up to again 250 ℃ after the input.In addition, the trivalent alcohol usage quantity is: relatively used 1 mole of the carboxyl of gum resin, the amount of hydroxyl groups in the trivalent alcohol is equivalent to 0.89 mole.In the intensification, with the reflux exchanger with water separator toluene and water are discharged outside the reaction system, make reaction 8 hours at the state that is maintained at 250 ℃, keep 250 ℃ constant, reduced pressure in 60 minutes to carrying out in the four-hole boiling flask with 20mmHg with drawdown pump, produced thus offset printing printing ink rosin modified phenolic resin C1.175 ℃ of the fusing points of gained offset printing printing ink usefulness rosin modified phenolic resin C1, acid value 22mgKOH/g, heptane maximum permission quantity 9mL/g, weight-average molecular weight 80,000 is from the metal content 18ppm of catalyzer.This comparative example is the example of not using sulfonic acid catalyst.
Comparative example 2
(manufacturing of rosin modified phenolic resin C2 of offset printing printing ink)
Toward having installed agitator, having dropped into 800 parts of gum resin with the reflux exchanger of water separator and the removable flask of four-hole of thermometer, be heated to 170 ℃ while passing into nitrogen, above-mentioned gum resin is dissolved, 800 parts of polycondensate F-1 that make in Production Example 1 have been dropped into while stirring the gum resin that has become the state that dissolves toward this gum resin, heat up again after dropping into, until 215 ℃, under this temperature, drop into 40 parts of 20 parts of trivalent alcohols and tetramethylolmethanes, be warmed up to again 250 ℃ after the input.In addition, the total usage quantity of trivalent alcohol and tetramethylolmethane is: 1 mole of the relative carboxyl that has used gum resin, the amount of hydroxyl groups in trivalent alcohol and the tetramethylolmethane is equivalent to 0.77 mole.In the intensification, with the reflux exchanger with water separator toluene and water are discharged outside the reaction system, make reaction 4 hours at the state that is maintained at 250 ℃, the removable flask contents of four-hole is taked out a part, when acid value becomes 50mgKOH/g, 2 parts of toluene sulfonic acides have been put in the removable flask of four-hole, then 250 ℃ of reactions 2 hours, keep 250 ℃ constant, reduced pressure in 60 minutes to carrying out in the four-hole boiling flask with 20mmHg with drawdown pump, produced thus offset printing printing ink rosin modified phenolic resin C2.150 ℃ of the fusing points of gained offset printing printing ink usefulness rosin modified phenolic resin C2, acid value 31mgKOH/g, heptane maximum permission quantity 14mL/g, weight-average molecular weight 30,000 is from the metal content 25ppm of catalyzer.This comparative example is offset printing printing ink with the acid value of rosin modified phenolic resin is the example of height.
Comparative example 3
(Production Example 5: the manufacturing of polycondensate F-5)
In the four-hole boiling flask of having installed agitator, reflux condensing tube and thermometer, drop into 1500 parts of 2200 parts of p-nonyl phenols, 652 parts of 92% Paraformaldehyde 96s and toluene, after the four-hole boiling flask content has been heated to 50 ℃, under this temperature, in four-hole boiling flask, dropped into 50 parts in 48% sodium hydroxide.The four-hole boiling flask content was heated to 80 ℃ of reactions after 6 hours, with in 40 parts of 35% hydrochloric acid with the four-hole boiling flask content, wash with 500 parts of water.After leaving standstill 6 hours, remove water layer, obtained thus polycondensate F-5.
(manufacturing of rosin modified phenolic resin C3 of offset printing printing ink)
Toward having installed agitator, having dropped into 800 parts of gum resin with the reflux exchanger of water separator and the removable flask of four-hole of thermometer, be heated to 170 ℃ while passing into nitrogen, above-mentioned gum resin is dissolved, 650 parts of polycondensate F-5 that make in Production Example 5 have been dropped into while stirring the gum resin that has become the state that dissolves toward this gum resin, heat up again after dropping into, until 215 ℃, under this temperature, drop into 40 parts of 20 parts of trivalent alcohols and tetramethylolmethanes, be warmed up to again 250 ℃ after the input.In addition, the total usage quantity of trivalent alcohol and tetramethylolmethane is: 1 mole of the relative carboxyl that has used gum resin, the amount of hydroxyl groups in trivalent alcohol and the tetramethylolmethane is equivalent to 0.77 mole.In the intensification, with the reflux exchanger with water separator toluene and water are discharged outside the reaction system, make reaction 4 hours at the state that is maintained at 250 ℃, the removable flask contents of four-hole is taked out a part, when acid value becomes 50mgKOH/g, 2 parts of toluene sulfonic acides have been put in the removable flask of four-hole, then 250 ℃ of reactions 2 hours, keep 250 ℃ constant, reduced pressure in 60 minutes to carrying out in the four-hole boiling flask with 20mmHg with drawdown pump, produced thus offset printing printing ink rosin modified phenolic resin C3.150 ℃ of the fusing points of gained offset printing printing ink usefulness rosin modified phenolic resin C3, acid value 22mgKOH/g, heptane maximum permission quantity 14mL/g, weight-average molecular weight 7.8 ten thousand is from the metal content 400ppm of catalyzer.This comparative example is offset printing printing ink with the metal content from catalyzer of rosin modified phenolic resin is the example of height.
Comparative example 4
(manufacturing of rosin modified phenolic resin C4 of offset printing printing ink)
Toward having installed agitator, having dropped into 800 parts of gum resin with the reflux exchanger of water separator and the removable flask of four-hole of thermometer, be heated to 170 ℃ while passing into nitrogen, above-mentioned gum resin is dissolved, drop into successively 2 parts of 870 parts of 40 parts of 10 parts of polycondensate F-3, trivalent alcohols, tetramethylolmethanes making in Production Example 3 and p-methyl benzenesulfonic acids while stirring the gum resin that become the state that dissolves toward this gum resin, be warmed up to 250 ℃ after the input.In addition, the total usage quantity of trivalent alcohol and tetramethylolmethane is: 1 mole of the relative carboxyl that has used gum resin, the amount of hydroxyl groups in trivalent alcohol and the tetramethylolmethane is equivalent to 0.64 mole.In the intensification, with the reflux exchanger with water separator toluene and water are discharged outside the reaction system, make reaction 2 hours at the state that is maintained at 250 ℃, keep 250 ℃ constant, reduced pressure in 60 minutes to carrying out in the four-hole boiling flask with 20mmHg with drawdown pump, produced thus offset printing printing ink rosin modified phenolic resin C4.160 ℃ of the fusing points of gained offset printing printing ink usefulness rosin modified phenolic resin C4, acid value 21mgKOH/g, heptane maximum permission quantity 19mL/g, weight-average molecular weight 20,000 is from the metal content 16ppm of catalyzer.This comparative example is the example that allows offset printing printing ink react simultaneously with the raw material of rosin modified phenolic resin.
Comparative example 5
(manufacturing of rosin modified phenolic resin C5 of offset printing printing ink)
Toward having installed agitator, having dropped into 800 parts of gum resin with the reflux exchanger of water separator and the removable flask of four-hole of thermometer, be heated to 170 ℃ while passing into nitrogen, above-mentioned gum resin is dissolved, 870 parts of polycondensate F-3 that make in Production Example 3 have been dropped into while stirring the gum resin that has become the state that dissolves toward this gum resin, heat up again after dropping into, until 215 ℃, under this temperature, drop into 30 parts of 50 parts of trivalent alcohols and tetramethylolmethanes, be warmed up to again 250 ℃ after the input.In addition, the total usage quantity of trivalent alcohol and tetramethylolmethane is: 1 mole of the relative carboxyl that has used gum resin, the amount of hydroxyl groups in trivalent alcohol and the tetramethylolmethane is equivalent to 1.06 moles.In the intensification, with the reflux exchanger with water separator toluene and water are discharged outside the reaction system, make reaction 4 hours at the state that is maintained at 250 ℃, the removable flask contents of four-hole is taked out a part, when acid value becomes 50mgKOH/g, 2 parts of toluene sulfonic acides have been put in the removable flask of four-hole, then 250 ℃ of reactions 2 hours, keep 250 ℃ constant, reduced pressure in 60 minutes to carrying out in the four-hole boiling flask with 20mmHg with drawdown pump, produced thus offset printing printing ink rosin modified phenolic resin C5.179 ℃ of the fusing points of gained offset printing printing ink usefulness rosin modified phenolic resin C5, acid value 20mgKOH/g, heptane maximum permission quantity 12mL/g, weight-average molecular weight 120,000 is from the metal content 15ppm of catalyzer.This comparative example is such example: aspect addition, the contained carboxyl of rosin based is 1 mole relatively, and the amount of hydroxyl groups of polyvalent alcohol is greater than 0.9 mole.
Table 1
| ? | Resin 1 | Resin 2 | Resin 3 | Resin 4 | Resin 5 | Resin 6 | Resin C1 | Resin C2 | Resin C3 | Resin C4 | Resin C5 |
| Fusing point | 150 | 180 | 160 | 185 | 175 | 174 | 175 | 150 | 150 | 160 | 179 |
| Acid value | 20 | 18 | 19 | 21 | 20 | 21 | 22 | 31 | 22 | 21 | 20 |
| HT | 21 | 15 | 17 | 13 | 16 | 20 | 9 | 14 | 14 | 19 | 12 |
| Mw | 8 | 1.3 | 2 | 2 | 10 | 2.8 | 8 | 3 | 7.8 | 2 | 12 |
| Content | 23 | 12 | 10 | 10 | 16 | 20 | 18 | 25 | 400 | 16 | 15 |
The mark implication is as follows in the table 1.
Resin: offset printing printing ink rosin modified phenolic resin
HT: heptane maximum permission quantity
Mw: weight-average molecular weight
Content: the content (ppm) of employed metal from catalyzer when making polycondensate
The making of varnish of offset printing printing ink
30 parts of 40 parts of crushed materials, soybean oil obtaining after embodiment 1～6 and each offset printing printing ink of comparative example 1～5 gained are pulverized with rosin modified phenolic resin finely and AF-5 Solvent30 part are dropped into the removable flask of four-hole, pass into the temperature of the removable flask contents of nitrogen one edge height four-hole on one side, stirred the foregoing thing 1 hour on one side in 190 ℃ of heating on one side, then cooling.Dissolve 0.7 part of ALCH (Kawaken Fine Chemicals Co. with 0.7 part of AF-5 Solvent under being added on 130 ℃, Ltd. 1.4 parts of the solution that jelling agent processed) obtains, so that the viscosity of the removable flask contents of four-hole (the E type viscometer with Japan smart machine Co., Ltd. system is measured under 25 ℃) becomes 10～35Pas, be warmed up to 160 ℃, in this temperature insulation 1 hour.When the viscosity of the removable flask contents of four-hole is not in 10～35Pas, be by append AF-5 Solvent or ALCH obtain offset printing printing ink with varnish 1～6 (having used respectively the offset printing printing ink rosin modified phenolic resin of embodiment 1～6), offset printing printing ink with varnish C1～C5's (having used respectively the offset printing printing ink rosin modified phenolic resin of comparative example 1～5).As shown in table 2 with the result that varnish carries out the LITHOTRONIC emulsion test as follows to gained offset printing printing ink.
(LITHOTRONIC emulsion test)
Get offset printing printing ink and test with LITHOTRONIC emulsion test instrument (NOVOCONTROL company system) with varnish 25g, obtain EC (%) and moment of torsion rate of rise (%) by defined terms of the present invention.Be preferably more than 1.0 below 4.0, this is the cause of reaching suitable resistance to emulsion because not causing the problem of the bad and Over emulsfication of initial stage emulsification.
Table 2
| ? | Varnish 1 | Varnish 2 | Varnish 3 | Varnish 4 | Varnish 5 | Varnish 6 | Varnish C1 | Varnish C2 | Varnish C3 | Varnish C4 | Varnish C5 |
| EC | 199 | 156 | 159 | 148 | 180 | 126 | 209 | 132 | 120 | 135 | 220 |
| Rate of rise | 102 | 155 | 250 | 201 | 118 | 200 | 188 | 158 | 74 | 100 | 200 |
| Long-pending | 2.0 | 2.4 | 4.0 | 3.0 | 2.1 | 2.5 | 3.9 | 2.1 | 0.9 | 1.4 | 4.4 |
" varnish " expression offset printing printing ink varnish in the table 2.
The mark implication is as follows in the table 2.
EC: maximum emulsification rate (EC (Emulsification Capacity: the % of unit)
Rate of rise: moment of torsion rate of rise
Long-pending: maximum emulsification rate and moment of torsion rate of rise are long-pending
(modulation of offset printing printing ink)
It is black with 18 parts of usefulness three rollings of Co., Ltd.'s ZAB120 red processed of refining each 54 parts of varnish C1～C5 and large day with varnish 1～6 and offset printing printing ink to get above-mentioned offset printing printing ink, add AF-5Solvent and gelling varnish (gel varnish), until total amount reaches 100 parts, but also suitably adjust, so that 25 ℃ adhesivity (tackiness) becomes 9.0, so obtain offset printing printing ink 1～6 and offset printing printing ink C1～C5.As shown in table 3 to the gained ink evaluation.Offset printing ink performance test method is as follows.
(ink performance test)
Resistance to emulsion: get offset printing printing ink 25g and test with LITHOTRONIC emulsion test instrument (NOVOCONTROL company system), it is long-pending to obtain EC and moment of torsion rate of rise.At this, except stirring velocity was changed to 800rpm from 1200rpm, test conditions was the same with the LITHOTRONIC emulsion test condition of varnish with the offset printing printing ink of the present invention's regulation.Be preferably more than 0.7 below 4.0, this is the cause of reaching suitable resistance to emulsion because not causing the problem of the bad and Over emulsfication of initial stage emulsification.
Zero: 0.7 above below 4.0
△: surpass 4.0 and during less than 7.0, or 0.3 above and less than 0.7
*: more than 7.0, or less than 0.3
Fly China ink (misting): allow offset printing printing ink be attached to the smart machine INK-O-METER processed of Co., Ltd. of Japan, make roller group rotation, judge the at that time state that disperses of offset printing printing ink by the dirty situation of the blank sheet of paper around the visual INK-O-METER.
Zero: almost do not have dirty, out of question in the practicality.
△: a part has obviously dirty.
*: dirty obvious.
Mobile: offset printing printing ink 1.3mL is placed sheet glass, and 70 degree tilt, and the mobile distance (mm) after a day is judged.If 200～300mm then reaches the equilibrium of dirty generation and printing ink easy mobility easily, so be preferred.
Zero: below the above 300mm of 200mm
△: surpass 300mm but not enough 400mm, or the above and not enough 200mm of 100mm
*: more than the 400mm, or not enough 100mm
Table 3
| ? | Printing ink 1 | Printing ink 2 | Printing ink 3 | Printing ink 4 | Printing ink 5 | Printing ink 6 | Printing ink C1 | Printing ink C2 | Printing ink C3 | Printing ink C4 | Printing ink C5 |
| Resistance to emulsion | ○ | ○ | ○ | ○ | ○ | ○ | × | △ | × | × | × |
| Fly China ink | ○ | ○ | ○ | ○ | ○ | ○ | ○ | △ | ○ | × | ○ |
| Mobile | ○ | ○ | ○ | ○ | ○ | ○ | × | × | × | ○ | × |
" printing ink " expression offset printing printing ink in the table 3.
From the comparing result of the embodiment of table 1～3 and comparative example as can be known: by adopting offset printing printing ink rosin modified phenolic resin of the present invention, can obtain being suitable for the dirty few flexographic ink of offset printing high speed, forme and print.
Practicality
Be suitable for the dirty few flexographic ink of offset printing high speed, forme and print by adopting offset printing printing ink rosin modified phenolic resin of the present invention, can providing.
Claims (3)
1. an offset printing printing ink rosin modified phenolic resin manufacture method is characterized in that, this resin be from the polycondensate of rosin based, alkylphenol and aldehyde and polyol derivative, the rosin modified phenolic resin of acid value below 30; Make after the reaction of rosin based and above-mentioned polycondensate, add polyvalent alcohol, and 1 mole of the contained carboxyl of the relative rosin based of amount of hydroxyl groups that makes addition satisfy polyvalent alcohol is more than 0.5 mole below 0.9 mole; And the interpolation sulfonic acid catalyst makes with the reacted rosin based of above-mentioned polycondensate and polyvalent alcohol and reacts in the presence of sulfonic acid catalyst; The metal maximum level is 150ppm.
2. by offset printing printing ink rosin modified phenolic resin manufacture method claimed in claim 1, it is characterized in that the catalyzer that above-mentioned metal uses during from the above-mentioned polycondensate of manufacturing.
3. an offset printing printing ink varnish manufacture method is dissolved in plant oil and/or printing ink solvent to offset printing printing ink according to claim 1 and 2 with the resulting offset printing printing ink of rosin modified phenolic resin manufacture method with rosin modified phenolic resin at least; In the LITHOTRONIC emulsion test, maximum emulsification rate and moment of torsion rate of rise long-pending be more than 1.0 below 4.0.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2010/006916 WO2012070093A1 (en) | 2010-11-26 | 2010-11-26 | Process for manufacturing rosin-modified phenol resin for offset printing ink and process for manufacturing varnish for offset printing ink |
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| CN103080246A true CN103080246A (en) | 2013-05-01 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103305079A (en) * | 2013-06-28 | 2013-09-18 | 江苏海田技术有限公司 | Alcohol-based resin coating |
| CN113122047A (en) * | 2019-12-30 | 2021-07-16 | 苏州青田新材料有限公司 | Preparation method of offset printing ink resin |
| CN114854244A (en) * | 2022-04-27 | 2022-08-05 | 北京金印联国际供应链管理有限公司 | Environment-friendly offset printing ink and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6284033B2 (en) * | 2014-09-11 | 2018-02-28 | 荒川化学工業株式会社 | Method for producing rosin-modified phenolic resin for offset printing ink, gel varnish for offset printing ink, and offset printing ink |
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| JP2004149735A (en) * | 2002-11-01 | 2004-05-27 | Arakawa Chem Ind Co Ltd | Resin composition for printing ink, resin varnish for printing ink, printing ink, and method for manufacturing them |
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| CN101475675A (en) * | 2009-01-06 | 2009-07-08 | 杭华油墨化学有限公司 | Resin for aromatic-free offset printing ink and preparation thereof |
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| JP2001279147A (en) * | 2000-03-29 | 2001-10-10 | Arakawa Chem Ind Co Ltd | Binder for offset printing ink, and offset printing ink |
| JP2008174645A (en) * | 2007-01-19 | 2008-07-31 | Toyo Ink Mfg Co Ltd | Method for producing metal foil stamp-printed matter and offset ink used for the same |
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| JP2004149735A (en) * | 2002-11-01 | 2004-05-27 | Arakawa Chem Ind Co Ltd | Resin composition for printing ink, resin varnish for printing ink, printing ink, and method for manufacturing them |
| CN1233680C (en) * | 2003-06-03 | 2005-12-28 | 山西省应用化学研究所 | Phenol-formaldehyde resin by colophony modified with alkyl phenol being mixed and its preparation method |
| JP2008274150A (en) * | 2007-05-01 | 2008-11-13 | Arakawa Chem Ind Co Ltd | Rosin-modified phenolic resin and rosin-modified phenolic resin for offset printing |
| CN101475675A (en) * | 2009-01-06 | 2009-07-08 | 杭华油墨化学有限公司 | Resin for aromatic-free offset printing ink and preparation thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103305079A (en) * | 2013-06-28 | 2013-09-18 | 江苏海田技术有限公司 | Alcohol-based resin coating |
| CN113122047A (en) * | 2019-12-30 | 2021-07-16 | 苏州青田新材料有限公司 | Preparation method of offset printing ink resin |
| CN114854244A (en) * | 2022-04-27 | 2022-08-05 | 北京金印联国际供应链管理有限公司 | Environment-friendly offset printing ink and preparation method thereof |
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