WO1996034922A1 - Vernis a encre, composition et procede de fabrication - Google Patents

Vernis a encre, composition et procede de fabrication Download PDF

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Publication number
WO1996034922A1
WO1996034922A1 PCT/US1995/005593 US9505593W WO9634922A1 WO 1996034922 A1 WO1996034922 A1 WO 1996034922A1 US 9505593 W US9505593 W US 9505593W WO 9634922 A1 WO9634922 A1 WO 9634922A1
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WO
WIPO (PCT)
Prior art keywords
varnish
ink
component
resin
solvent
Prior art date
Application number
PCT/US1995/005593
Other languages
English (en)
Inventor
Thomas J. Pennaz
John H. Burban
Original Assignee
Deluxe Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to US07/041,794 priority Critical patent/US5308390A/en
Priority to US08/092,741 priority patent/US5354367A/en
Priority to US08/092,392 priority patent/US5338351A/en
Priority to US08/120,175 priority patent/US5382282A/en
Priority to JP6508328A priority patent/JPH08501493A/ja
Priority to EP93922223A priority patent/EP0660805B1/fr
Priority to EP93922224A priority patent/EP0677090B1/fr
Priority to NZ256547A priority patent/NZ256547A/en
Priority to CA002144776A priority patent/CA2144776A1/fr
Priority to JP6508327A priority patent/JPH08501588A/ja
Priority to CA002144778A priority patent/CA2144778A1/fr
Priority to NZ256549A priority patent/NZ256549A/en
Priority to AU51301/93A priority patent/AU679693B2/en
Priority to CA002144777A priority patent/CA2144777A1/fr
Priority to AU51303/93A priority patent/AU693423B2/en
Priority to NZ256548A priority patent/NZ256548A/en
Priority to US08/210,049 priority patent/US5431721A/en
Priority to NO950966A priority patent/NO950966L/no
Priority to NO950965A priority patent/NO950965L/no
Priority to NO950967A priority patent/NO950967L/no
Priority to FI951246A priority patent/FI951246A/fi
Priority to FI951248A priority patent/FI951248A/fi
Priority to FI951247A priority patent/FI951247A/fi
Application filed by Deluxe Corporation filed Critical Deluxe Corporation
Priority to US08/434,886 priority patent/US5549741A/en
Priority to AU24349/95A priority patent/AU2434995A/en
Priority to PCT/US1995/005593 priority patent/WO1996034922A1/fr
Publication of WO1996034922A1 publication Critical patent/WO1996034922A1/fr

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Classifications

    • 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
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0073—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces
    • H05K3/0076—Masks not provided for in groups H05K3/02 - H05K3/46, e.g. for photomechanical production of patterned surfaces characterised by the composition of the mask

Definitions

  • the present invention relates to the field of ink compositions and varnishes and more particularly to ink varnishes and methods useful in the manufacture of ink compositions which exhibit desirable ink properties while at the same time substantially reducing or eliminating use of petroleum solvents.
  • the present invention also relates to ink varnishes having functional components providing the varnishes and resulting ink compositions with desirable properties including ink set, life, gloss, water washability and pigment dispersion, among others, and to methods of making such ink varnishes including an improved varnish cook cycle which maintains such functional components substantially in their functional form during the cook cycle.
  • Ink composition varnish and method of the present invention have applicability to most if not all of these prior processes, it has particular applicability to a lithographic printing process commonly referred to as offset lithography.
  • Traditional ink compositions are comprised of an ink varnish and a dispersed pigment.
  • Ink varnishes in turn include a resin component comprised of a hard resin, a liquid resin or a combination of hard and liquid resins, an oil component and a solvent component.
  • the oil and solvent components are comprised of materials such as vegetable oils, vegetable oil derivatives or combinations thereof, petroleum distillates and a variety of replacement solvents.
  • solvents in printing inks perform several functions. First, they provide solvency during the varnish manufacturing step by dissolving and carrying the various resins. Second, they are used during final adjustment of the ink varnish and composition to achieve the desired ink tack and viscosity. Third, solvents provide the primary means to set the ink while also controlling, to a major extent, the ink life.
  • the "set" of an ink reflects the time needed for a printed ink to set up via evaporation, reaction, absorption or the like to a point where it can be handled without smearing of the ink.
  • the "life” of an ink reflects the time during which the ink can remain on a print plate or other application equipment without setting or drying.
  • the properties of ink set and ink life are balanced. For example, conventional inks which set quickly tend to have a short life on the press, while inks which have a long life on the press generally take longer to set, especially on coated papers or other less porous substrates.
  • the degree of solution among the traditional ink varnish components also significantly affects various ink properties.
  • the solvents of choice in traditional ink varnish formulation have included petroleum distillates because of their ability to readily dissolve the conventional ink resins, because of their high volatility and because of their relatively low molecular weight.
  • the high volatility causes the solvents to evaporate quickly from the printed ink while the low molecular weight enables the petroleum distillates to readily absorb into the substrate immediately after printing.
  • Such evaporation and absorption causes the viscosity of the ink film to increase rapidly, thereby causing the ink to set.
  • ink compositions and varnishes have been developed in which all or a portion of the petroleum based solvents have been replaced with nonvolatile organic solvents.
  • the petroleum solvents have been replaced by various unsaturated fatty acid esters.
  • U.S. Patent No. 4,938,801 issued to Yoshioka a portion of the petroleum solvent has been replaced by a nonvolatile polar solvent which is then denatured.
  • the present invention provides an ink composition or varnish in which petroleum based solvents have been substantially reduced or eliminated and /or which contain functional components providing such composition and varnish with desirable ink properties such as ink set, life, gloss, tack, viscosity, pigment dispersion and water washability, among others.
  • the present invention also provides an improved ink manufacturing method or cook cycle which retains the beneficial properties of the nonvolatile solvents which have been selected to replace the petroleum solvents as well as the beneficial properties of other functional varnish components such as those providing water washability and /or pigment dispersibility.
  • Such improved cook cycle also substantially reduces energy requirements and ink varnish manufacturing time.
  • the present invention has particular applicability to ink compositions and varnishes which are substantially water insoluble in their printed form and which are usable in offset lithography.
  • ink compositions and varnishes usable in other printing processes are also within the scope of the present invention.
  • ink varnish cook cycles at elevated temperatures for extended periods of time are highly desirable when using petroleum based solvents, such cook temperatures and times are detrimental to many of the potential benefits of functional varnish components such as fatty acids, fatty acid esters and other relatively low molecular weight nonvolatile replacement solvents, water reducible resins to provide water washability,and acid functional resins to provide improved pigment dispersion, among others.
  • functional varnish components such as fatty acids, fatty acid esters and other relatively low molecular weight nonvolatile replacement solvents, water reducible resins to provide water washability,and acid functional resins to provide improved pigment dispersion, among others.
  • one aspect and object of the present invention is to provide an ink varnish cook cycle which involves a lower temperature and a significantly shorter cook time than conventional ink varnish cook cycles.
  • Many benefits of the replacement solvents and other functional components which are lost when conventional cooking techniques are employed are retained with the cook cycle of the present invention.
  • Such cook cycle also retains the beneficial properties of functional components such as water reducible resins, thereby facilitating the manufacture of water washable ink compositions and varnishes.
  • Another object of the present invention is to provide a varnish cook cycle for ink varnishes containing functional or reactive components in which the cook time and cook temperature are sufficiently long and high to dissolve or solvate the various varnish components, but sufficiently short and low to minimize reactions among the components, and thus retain the beneficial properties of such functional components.
  • a further object of the present invention is to provide an ink varnish cook cycle for an acid functional system in which the reduction in acid number of the ink varnish during the cook cycle is no greater than about 25% and /or in which the acid number of the ink varnish is reduced to no lower than about 25 during the cook cycle.
  • Another object of the present invention is to provide a low VOC lithographic ink composition or varnish embodying a hard resin with elevated acid functionality.
  • a further object of the present invention to provide a water insoluble ink composition or varnish having an absence or a minimal amount of petroleum based solvents and an acid number no less than about 25, preferably no less than about 45 and most preferably no less than about 60.
  • a further aspect of the present invention includes the use of various fatty acids, fatty acid esters and other low molecular weight nonvolatile solvents in combination with various functional resins including one or more water reducible resins to provide a substantially water insoluble ink composition which can be printed in its water insoluble form and washed up using aqueous based solutions.
  • the ink varnishes, compositions and method of the present invention have particular applicability to lithographic ink varnishes and compositions useful in the field of offset lithography. Accordingly, the preferred embodiment and method will relate principally to lithographic varnishes and compositions and ink properties important to offset lithography. The present invention is equally applicable, however, to other ink varnishes and compositions and other print processes including letter-press, gravure, flexographic and intaglio, among others.
  • fatty acids, fatty acid esters and other relatively low molecular weight nonvolatile solvents behave in a manner similar to that of petroleum solvents with many of the same benefits of petroleum solvents, as long as they remain substantially in their low molecular weight form and are not combined with other components of the varnish through esterification, transesterification or other reactions.
  • certain fatty acids, fatty acid esters and other low molecular weight nonvolatile solvents useful in the present invention are relatively mobile and reactive and that if they can be retained in their low molecular weight form, they essentially mimic the behavior of petroleum solvents by being readily absorbed into the printed substrate.
  • solvents in their low molecular weight form are hydrophilic, they are, in many cases, more readily absorbed, thus resulting in set times comparable to those achieved through the use of petroleum solvents.
  • the term "functional component" of a varnish means a varnish component having one or more of a variety of desired functional properties such as, among others, mobility, hydrophilicity, water reducibility, pigment dispersibility and resin solubility. Such functionality is often exhibited in a functional component because of the presence of various functional groups such as ester linkages, carboxyl or acid groups (COOH), hydroxyl groups (OH) or amine groups (NH 3 ). The preferred embodiment and method, however, will be described with respect to an acid functional system.
  • Esterification reactions are well known and involve the reaction of carboxyl groups and hydroxyl groups present on the resins, oils and solvents to form an ester linkage and thus join smaller molecules together into larger molecules.
  • Transesterification reactions involve the attack of existing ester linkages by carboxyl or hydroxyl functional materials.
  • the acid group cleaves the existing ester bond and is reattached to the resin by formation of a new ester group.
  • the potential for both esterification and transesterification reactions to occur increases rapidly as the acid number of the varnish and its components is increased.
  • esterification and other reactions involving the low molecular weight nonvolatile solvents or other functional components occur readily during conventional cook cycles, thus diminishing many of the benefits of such components.
  • esterification and other reactions during a varnish cook cycle can be followed by monitoring the acid number, viscosity and tack of the varnish as it cooks.
  • the acid number of a particular material is one accepted measure of acid functionality or the number of free acid or carboxyl groups (COOH) groups available in that material for reaction. Tests are known in the art for determining the acid number of a material. Acid number is expressed as the amount of potassium hydroxide (KOH) in milligrams (mg) required to neutralize one gram of the material tested. Since the esterification reaction consumes acid, the acid number of the varnish decreases as the cook cycle, and thus esterification, proceeds.
  • KOH potassium hydroxide
  • the reduction of the acid number of the varnish during the cook cycle can be determined by comparing the acid number at the beginning and at the end of the cook cycle.
  • the acid number at the beginning can be determined by calculation (the theoretical acid number) or by measurement.
  • the beginning of the cook cycle is the point at which all of the resin is dissolved in the solvent and oil.
  • the acid number at the end of the cook cycle is determined by measurement.
  • the process of the present invention involves a cook cycle which results in a minimum reduction of the acid number of the varnish, preferably by less than 25%, more preferably less than 10% and most preferably less than 5%. Accordingly, the resulting loss or reduction of acid number during the cook cycle provides a quantitative method by which esterification and other reactions can be monitored and thus use of the present invention determined.
  • esterification and transesterification reactions can also cause changes in viscosity and tack of the varnish as it cooks
  • the extent to which such reactions occur can often be determined by monitoring the viscosity and/or tack.
  • the extent of reaction by the hydroxy or amine functional components during a cook cycle can be followed by monitoring the respective hydroxy or amine number of the varnish while it cooks.
  • the ink varnishes in accordance with the present invention and to which the method of the present invention is applicable are those which are substantially water insoluble and intended to be printed in their water insoluble form.
  • the ink varnishes of the present invention are oleoresinous varnishes which are generally used to produce quick set, heat set and various other drying inks which set and /or dry by oxidation, absorption into the substrate, and/or solvent evaporation.
  • the ink varnish is comprised principally of resins, oils and solvents. A general requirement of the resin, oil and solvent components is that they be compatible with one another. In other words, capable of solvation or miscibility.
  • the resin component of the ink varnish of the present invention functions among other things as a film former to bind the varnish and pigment together and, when the ink drys, to bind the same to the receiving substrate.
  • the resin component also contributes to the properties of hardness, gloss, adhesion and flexibility of the ink.
  • the resin component is commonly comprised of a hard resin component and/or a liquid resin component, but can comprise various other compositions and resins as well.
  • the ink varnish of the present invention also comprises both a hard resin and a liquid resin; thus, it is at least a two resin component system. However, this is not a requirement.
  • the hard resins are normally solid at room temperatures and typically fall into two principal classes: the modified rosin ester resins and the modified hydrocarbon resins.
  • Various hard resins or hard resin combinations or blends can be, and have been, utilized in the ink varnish of the present invention provided such resins are compatible with the other components of the varnish.
  • compatibility means generally soluble or miscible with one another.
  • Hard resins usable in the ink varnishes of the present invention may be comprised of natural or processed resins such as rosins, rosin esters, maleic modified resins, rosin modified fumaric resins, dimerized and polymerized rosins, asphalts such as gilsonite and like, phenolics, rosin modified phenolics, terpenes, polyamides, cyclized rubber, acrylics, hydrocarbons and modified hydrocarbons. Also included among the available hard resins are those identified in The Printing Ink Manual, 4th Ed. (1988) edited by R.H. Leach and published by Van Nostrand Reinhold, the substance of which is incorporated herein by reference.
  • hard resins usable in ink varnishes are usually cooked so as to have substantially all of the acid or carboxyl groups (COOH) reacted with all or substantially all of the hydroxyl (OH) groups. This results in a resin having relatively low acid functionality and thus low reactivity with an acid number less than 30 and often less than 20.
  • these low acid functional resins can be used in the present invention, improved compatibility and solubility with the oils, nonvolatile solvents and other functional varnish components of the present invention can be achieved by using hard resins with elevated acid functionality, and in particular those exhibiting acid numbers greater than 30, more preferably greater than 40, and most preferably greater than 50 or greater than 80.
  • the hard resins generally have melting temperatures greater than about 300° F (149° C).
  • the hard resin comprises at least about 5% by weight of the varnish and more preferably at least about 10% by weight.
  • the liquid resin component for a two resin component ink varnish of the present invention functions to form the varnish or ink composition into a cohesive material and, upon printing, to bond the pigment to the receiving substrate.
  • the liquid resin component is typically not solid, but is a viscous liquid.
  • Liquid resins usable in accordance with the present invention can include alkyds, polyesters, maleic modified drying oils and styrenated epoxy esters together with various other liquid resins known to those in the art and also those identified in The Printing Ink Manual, supra, the substance of which is incorporated herein by reference.
  • the liquid resins may also include, if desired, functional resins such as water reducible resins for providing the ink with water washability as disclosed in U.S. Patent No. 5,338,351 dated August 16, 1994.
  • functional resins such as water reducible resins for providing the ink with water washability as disclosed in U.S. Patent No. 5,338,351 dated August 16, 1994.
  • the substance of the entirety of such patent and particularly the disclosure and examples relating to the water reducible liquid resins is incorporated herein by reference.
  • the term water reducible defines a property of a resin or composition which enables such resin or composition to be substantially water insoluble under certain conditions (preferably pH related) and capable of being or becoming water soluble or water washable or dispersible under certain other conditions (preferably pH related).
  • the term water reducible defines a resin or composition whose water solubility behavior is pH dependent, with such resin or composition being water insoluble under certain acidic conditions and water washable under certain alkaline conditions, or vice versa.
  • water washable refers to a substantially water insoluble ink composition or varnish which can be printed in its water insoluble form, but cleaned up or washed with an aqueous solution.
  • the most preferred resins are the water reducible alkyds and water reducible polyesters. All of the above are compatible with castor oil except for Cargill's modified linseed oil 73-7319 which is compatible with linseed and soya oil and Magie solvent. Cargill's short oil alkyd 74-7451 is additionally compatible with linseed and castor oils.
  • water solubility or washability characteristics depend on the pH of the aqueous solution with which such compositions come into contact.
  • such resin and the resulting compositions or varnishes are water insoluble at a first acidic pH level less than 7.0.
  • the pH of the solution to which the composition will come into contact in its insoluble form is between about 3.0 and 6.5 and most preferably between about 4.0 and 5.5.
  • the second pH level at which the water reducible resin and resulting ink composition or varnish becomes water soluble or washable is an alkaline pH having sufficient basic strength to substantially neutralize the acid groups of the water reducible resin.
  • the water reducible resin should comprise at least about 5% by weight of the varnish, more preferably about 5% to 60% by weight and most preferably about 10% to 40% by weight.
  • the water reducible resins of the type described above are acid functional, with such acid functionality being a principle factor in providing such resins with their water reducible properties. Acid numbers of these resins are generally above 25 and preferably above 30. Because of this functionality, employment of conventional cook cycles will tend to result in esterification and other reactions, thus diminishing or eliminating the " desired water reducible properties. Accordingly, the cook cycle of the present invention preferably employs cook times and cook temperatures which minimize or eliminate esterification and other reactions involving the water reducible resin components.
  • the benefits of water washability can be achieved by using water reducible resins along with other conventional varnish components.
  • a water washable ink varnish in accordance with the present invention includes both water reducible resins for water washability and low molecular weight nonvolatile solvents such as those described below for improved ink set, life and other properties.
  • the oil and solvent portion of the ink varnish of the present invention can be comprised of various oils and solvents common in ink formulation including, among others, various vegetable oils such as linseed oil, soya oil, castor oil and rung oil, various vegetable oil derivatives and various relatively low molecular weight nonvolatile solvents such as fatty acids and fatty acid esters.
  • the solvent portion of the ink varnish may also include a limited amount of petroleum based solvents if desired, however, preferably, the use of petroleum based solvents is eliminated entirely or reduced as much as possible for the reasons discussed above.
  • the low molecular weight nonvolatile solvents should comprise between about 5% to 75% by weight of the ink varnish, more preferably about 10% to 40% by weight and most preferably about 15% to 30% by weight.
  • nonvolatile solvents useful in the composition of the present invention assume a nonvolatile or substantially nonvolatile state at ambient temperatures.
  • nonvolatile is intended to mean liquids which do not evaporate appreciably under ambient conditions or have a vapor pressure less than 1.0 mmHg at 25°C.
  • solvent groups which bring about acid base reaction or hydrogen bonding such as carboxyl group, amino group, hydroxyl group, ether group and amide group.
  • liquid aliphatic amines such as aliphatic monoamine, ethylene diamine, propylene, diamine and alkyl derivatives thereof
  • polyalcohol such as aliphatic alcohol of C 5 or above, ethylene glycol, diethylene glycol, propylene glycol, alcohol ether thereof, aliphatic ether, glycerine, trimethylolpropane and pentaerythritol
  • other solvents including ketone such as cyclohexanone, ester and amine.
  • the low molecular weight nonvolatile solvents include those solvents having a molecular weight less than about 500 and more preferably less than 350. These solvents are sufficiently mobile and sufficiently hydrophilic so that they will be quickly absorbed into the printed substrate provided they are not subject to esterification, transesterification or other reactions during the varnish cook cycle. Many of the nonvolatile solvents such as the fatty acids have a relatively high acid functionality, with acid numbers greater than about 190. Thus, they are subject to both esterification and transesterification reactions. Others such as esters, however, have little or no acid functionality. Thus, these are subject principally to transesterification reactions.
  • the preferred components of the ink varnish are those considered to have a relatively high acid functionality as described above.
  • the use of high acid functional materials such as certain resins and the like are increasing in ink formulation, particularly as more functional nonvolatile solvents are being used.
  • Several potential advantages can be realized from such components including improved pigment dispersion, emulsification control and improved solubility between the acid functional resins and the acid functional solvents, among others.
  • water washability properties can be provided in an ink by using acid functional, water reducible resins.
  • the low VOC inks of the present invention have benefits even without water washability. It is believed that many of these potential advantages and properties are lost or significantly diminished, however, during conventional cook cycles as esterification and other reactions occur.
  • the cook cycle in accordance with the present invention involves cooking the various varnish components at temperatures and for a time period which is sufficient to dissolve the resins into the oils and solvents, but not at temperatures or times which will result in any appreciable esterification or transesterification, thereby maintaining the various functional components substantially in their functional form.
  • the cook cycle of the present invention includes cooking the varnish components in a cook reactor or other vessel at a temperature slightly above the melting point of the highest melting point hard resin.
  • the melting point of the highest melting point resin will vary from varnish to varnish.
  • the cook temperature should be no more than about 50° F. (28° C) higher than the highest melting point resin, preferably no more than 20° F (11° C) and most preferably no more than about 10° F (6° C).
  • the materials are then held at or about this temperature with agitation for a time period which is preferably less than one hour, more preferably less than 30 minutes and most preferably for a period of about 5-20 minutes.
  • the cook conditions, specifically temperature and time should be sufficiently high and long to melt the resins and to dissolve the various varnish components but sufficiently low and short to limit esterification or other reactions as much as possible, thereby maintaining the nonvolatile solvents and other functional components substantially in their unreacted and functional form.
  • the cook temperature and cook time should be low and short enough to limit the reduction of acid number during the cook cycle to no more than 25%, preferably no more than 10% and most preferably no more than about 5%.
  • the resulting ink varnish for a water insoluble ink composition of the present invention preferably exhibits an acid number greater than 60, more preferably greater than 45 and most preferably greater than 25.
  • the temperature of the components in the reactor is preferably cooled quickly so that if the temperature of such components is greater than about 300° F (149° C), such temperature drops below this level within about 5 minutes. This may be accomplished either by appropriate heat exchanger or cooling means or by holding back a portion of the liquid components of the varnish (preferably oils and /or solvents) and leaving them at room temperature. Then, at the end of the cook cycle, these ingredients are combined with the heated components for purposes of quickly cooling such heated components. About 5% to 30% by weight of the oils and solvents and preferably about 10% to 20% of the oils and solvents may be withheld from the cook cycle for this purpose.
  • the specific cook temperatures, cook times, cool times and techniques can vary, and will in fact vary, depending upon the particular components of the system.
  • the temperature and duration of the cook cycle should be sufficiently low and sufficiently short so as to minimize or eliminate esterification or other reactions among the varnish components.
  • at least about 70% of such solvents will remain in their low molecular weight form during the cook cycle.
  • an ink composition is made by combining the ink varnish with the desired pigment and dispersing the pigment throughout the varnish. Technologies and methods for pigment dispersion are well known to those knowledgeable in the art and any of these methods can be used in preparing the ink composition in accordance with the present invention.
  • One accepted method of dispersing color pigment in ink varnish which is applicable to varnishes of the present invention is a process known as flushing. To practice this process a pigment/water slurry composed of about 30% pigment and 70% water and commonly referred to as presscake is mixed with the varnish with sufficient energy to cause the varnish to replace the water. The displaced water is then decanted off, leaving the pigment dispersed in the varnish. The resulting product is referred to in the art as a color flush containing a high concentration of pigment.
  • the ink composition is then produced by combining the flush with a letdown varnish and/or other additives and solvent to achieve desired physical properties.
  • Example 1 A series of experiments was conducted to analyze the effect of cook parameters (temperature and time) on varnish and ink properties in which the varnish contains a water reducible resin and a low molecular weight nonvolatile solvent.
  • the water reducible resin is a short oil alkyd (Cargill 74- 7451) and the nonvolatile solvent is a fatty acid, namely oleic acid having a molecular weight of 282.
  • Varnish was produced by combining the resins and oil components together and heating in a one liter laboratory reactor fitted with a thermocouple and high-speed agitation. The heating mantle was fitted with temperature control to maintain constant temperature.
  • a stopwatch was used to monitor the cook time. At cook times of 15 minutes, 30 minutes and 120 minutes, 300 gms. of varnish were removed for analysis. When samples were removed, they were crash cooled in an ice bath to simulate rapid cooling. The acid number of each varnish sample was determined by titration with 0.1M potassium hydroxide in methanol. Phenolphthalein indicator was used to determine the endpoint.
  • Test inks were produced by adding 18% by weight of Raven 1500 (Columbian Chemical) pigment to the varnish samples.
  • the pigment was ground on a Buhler SDX600 three roll mill.
  • Ink viscosity (in poise) and yield value were measured with a laray viscometer (Ademel Lhomargy) using four drop times.
  • Ink tack was measured at 1 minute and 5 minute intervals on a Twig-Albert Model 106 inkometer at 90° F and 800 RPM. Set times were determined by the following procedure: 1. A drawdown was produced from the Akira proof press on King James cast coat stock.
  • aqueous wash solution comprised of 1% by weight sodium hydroxide, 2% by weight nonionic surfactant (Macol 19), 0.1% by weight EDTA and 96.9% by weight deionized water were determined by the following procedure:
  • the press was idled for one minute to evenly distribute the ink to all rollers.
  • a stopwatch was used to measure the time required to completely clean the rollers of all ink, with small additions of roller wash being added until all rollers were completely cleaned.
  • Oleic Acid (Emersol 214NF Henkel Inc.) 202 - 19.5%
  • Example 2 The printability of all ink samples was good. The samples exhibited varying degrees of acceptability of ink set and water washability as shown. Example 2
  • Example 2 comprised a series of experiments, identical to the procedures of example 1 except that the low molecular weight nonvolatile solvent was a fatty acid ester, namely Nirez 9012 from Arizona Chemical.
  • the fatty acid ester had a molecular weight of about 300.
  • the theoretical beginning acid value of the varnish was 34.74.
  • Fumaric Mod. Rosin (Unirez 8100, Union Camp) 100.72 230 6.1% Fumaric Mod. Rosin (Unirez 8200, Union Camp) 202.35 309 6.1%
  • Example 3 an ink varnish was produced by the process of the present invention and was then used to flush presscake to produce a color concentrate known as a flush.
  • An ink varnish having the composition set forth below was produced by cooking all ingredients except the oleic acid and linseed oil in a cook kettle.
  • the oleic acid and linseed oil were held out and maintained at room temperature.
  • the kettle was heated with the caster oil until a temperature of 250° F was reached.
  • the Unirez 8100 was then added and the heating continued with agitation.
  • the temperature reached 300° F, the alkyd, Unirez 8200 and Unirez 9405 were added with agitation.
  • the temperature was brought to 330° F and held for 15 minutes, after which the oleic acid and linseed oil were added to rapidly drop the temperature to 270° F. Cooling water was then circulated through cooling coils in the kettle to drop the temperature to 200°F.
  • Castor Oil (United Catalyst) - - 32.68% Oleic Acid (Emersol 214NF Henkel Inc.) 202 — 15.60% Linseed Oil (00 Reg. Litho, Degen Oil) - - 5.21%
  • Example 4 Because a color flush contains a higher concentration of pigment than is desired for an ink composition, production of an ink composition involves combining the flush with a letdown varnish together with other ink additives and additional solvent, if needed, to obtain an ink composition with the desired pigment concentration, viscosity and other physical properties.
  • Example 4 demonstrates the production of ink compositions of the process colors magenta, cyan and yellow by combining a flush prepared in accordance with the process of example 3 and a letdown varnish of the following composition also prepared in accordance with the process of example 3.
  • the process black ink composition having the following composition was produced by combining the resins, oils and solvents in accordance with the varnish cook process of Example 3. In such process, 10% of the fatty acid ester was held out and maintained at room temperature. The carbon black, alkali blue, wax and driers were then added and milled on a Buhler SDX600 three roll mill.
  • Paper gloss was 36 to 40. Set times and water washability were good for all inks.
  • Example 5 In example 5, the procedure of example 1 was followed for varnish composition employing a variety of nonvolatile solvents.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

La présente invention concerne une composition d'encre, un vernis et un procédé avec lequel la composition et le vernis comportent des niveaux réduits de solvants pétroliers tout en conservant des propriétés avantageuses de l'encre. L'invention concerne aussi un procédé de fabrication d'une composition d'encre et d'un vernis, ce procédé incluant un cycle de cuisson qui réduit au minimum, ou élimine, l'estérification et d'autres réactions impliquant les composants fonctionnels de la composition et du vernis.
PCT/US1995/005593 1992-09-17 1995-05-04 Vernis a encre, composition et procede de fabrication WO1996034922A1 (fr)

Priority Applications (26)

Application Number Priority Date Filing Date Title
US07/041,794 US5308390A (en) 1992-09-17 1993-04-01 Ink composition and method of making and using such composition
US08/092,741 US5354367A (en) 1992-09-17 1993-07-14 Radiation curable ink composition and method of making and using such composition
US08/092,392 US5338351A (en) 1992-09-17 1993-07-14 Ink composition and method of making, using and recovering such composition
US08/120,175 US5382282A (en) 1992-09-17 1993-09-13 Ink composition and method of making, using and recovering such composition
NZ256548A NZ256548A (en) 1992-09-17 1993-09-15 Process for cleaning up a water insoluble coating composition by adjusting the ph and washing
EP93922224A EP0677090B1 (fr) 1992-09-17 1993-09-15 Composition d'encre et procede de fabrication, d'utilisation et de recuperation de cette composition
NZ256547A NZ256547A (en) 1992-09-17 1993-09-15 Composition for removing a water insoluble composition comprises a solubility controlling component (changing solubility according to ph) and a diluent; use of a composition including the above for cleaning
CA002144776A CA2144776A1 (fr) 1992-09-17 1993-09-15 Encre et methode de fabrication, d'utilisation et de recuperation de cette encre
JP6508327A JPH08501588A (ja) 1992-09-17 1993-09-15 油性組成物の洗浄法およびそれに用いる組成物
CA002144778A CA2144778A1 (fr) 1992-09-17 1993-09-15 Methode de nettoyage d'eau usee et recuperation des contaminants a partir de cette eau
NZ256549A NZ256549A (en) 1992-09-17 1993-09-15 Ink compositions incorporating a water reducible resin whose water solubility is ph dependent; making, using and recovering such compositions
AU51301/93A AU679693B2 (en) 1992-09-17 1993-09-15 Oil based composition clean up method and composition for use therein
CA002144777A CA2144777A1 (fr) 1992-09-17 1993-09-15 Methode de lavage d'une composition a base d'hydrocarbures; melange utile a cette fin
JP6508328A JPH08501493A (ja) 1992-09-17 1993-09-15 廃水を浄化する方法及びそれから汚染物を回収する方法
EP93922223A EP0660805B1 (fr) 1992-09-17 1993-09-15 Procede d'epuration d'eaux residuaires et de recuperation de contaminants contenus dans les eaux residuaires
AU51303/93A AU693423B2 (en) 1992-09-17 1993-09-15 Ink composition and method of making, using and recovering such composition
US08/210,049 US5431721A (en) 1992-09-17 1994-03-17 Ink varnish and composition and method of making the same
NO950966A NO950966L (no) 1992-09-17 1995-03-14 Fremgangsmåte til fjerning av oljebaserte materialer, samt preparat til gjennomföring av fremgangsmåten
NO950965A NO950965L (no) 1992-09-17 1995-03-14 Fremgangsmåte til rensing av avlöpsvann, samt gjenvinning av urenheter fra slikt vann
NO950967A NO950967L (no) 1992-09-17 1995-03-14 Blekkpreparat samt fremgangsmåte til fremstilling, anvendelse og gjenvinning derav
FI951246A FI951246A (fi) 1992-09-17 1995-03-16 Menetelmä öljypohjaisen koostumuksen puhdistamiseksi ja menetelmässä käytettävä koostumus
FI951248A FI951248A (fi) 1992-09-17 1995-03-16 Painovärikoostumus ja menetelmä koostumuksen valmistamiseksi, käyttämiseksi ja talteenottamiseksi
FI951247A FI951247A (fi) 1992-09-17 1995-03-16 Menetelmä jäteveden puhdistamiseksi ja epäpuhtauksien talteenottamiseksi siitä
US08/434,886 US5549741A (en) 1992-09-17 1995-05-04 Ink varnish composition
AU24349/95A AU2434995A (en) 1992-09-17 1995-05-04 Ink varnish and composition and method of making the same
PCT/US1995/005593 WO1996034922A1 (fr) 1995-05-04 1995-05-04 Vernis a encre, composition et procede de fabrication

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1995/005593 WO1996034922A1 (fr) 1995-05-04 1995-05-04 Vernis a encre, composition et procede de fabrication

Publications (1)

Publication Number Publication Date
WO1996034922A1 true WO1996034922A1 (fr) 1996-11-07

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Country Link
WO (1) WO1996034922A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005066292A1 (fr) * 2003-12-31 2005-07-21 Sun Chemical Corporation Encres heatset pour rotative offset a faible teneur en composes organiques volatils
EP2426721A1 (fr) * 2009-04-27 2012-03-07 DIC Corporation Composition d'encre pour former un film d'écran vis-à-vis de la lumière pour un élément semi-conducteur organique, procédé de formation d'un film d'écran vis-à-vis de la lumière et élément de transistor organique ayant un film d'écran vis-à-vis de la lumière

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4938801A (en) * 1987-03-31 1990-07-03 Taniguchi Ink Manufacturing Co., Ltd. Printing inks
US5173113A (en) * 1991-03-12 1992-12-22 Topez Company Composition for ink vehicles and protective coatings
US5178672A (en) * 1991-04-08 1993-01-12 Canadian Fine Color Company Limited Printing compositions
US5338351A (en) * 1992-09-17 1994-08-16 Deluxe Corporation Ink composition and method of making, using and recovering such composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4938801A (en) * 1987-03-31 1990-07-03 Taniguchi Ink Manufacturing Co., Ltd. Printing inks
US5173113A (en) * 1991-03-12 1992-12-22 Topez Company Composition for ink vehicles and protective coatings
US5178672A (en) * 1991-04-08 1993-01-12 Canadian Fine Color Company Limited Printing compositions
US5338351A (en) * 1992-09-17 1994-08-16 Deluxe Corporation Ink composition and method of making, using and recovering such composition

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005066292A1 (fr) * 2003-12-31 2005-07-21 Sun Chemical Corporation Encres heatset pour rotative offset a faible teneur en composes organiques volatils
US7018453B2 (en) 2003-12-31 2006-03-28 Sun Chemical Corporation Low VOC web offset heatset inks
EP2426721A1 (fr) * 2009-04-27 2012-03-07 DIC Corporation Composition d'encre pour former un film d'écran vis-à-vis de la lumière pour un élément semi-conducteur organique, procédé de formation d'un film d'écran vis-à-vis de la lumière et élément de transistor organique ayant un film d'écran vis-à-vis de la lumière
EP2426721A4 (fr) * 2009-04-27 2012-10-03 Dainippon Ink & Chemicals Composition d'encre pour former un film d'écran vis-à-vis de la lumière pour un élément semi-conducteur organique, procédé de formation d'un film d'écran vis-à-vis de la lumière et élément de transistor organique ayant un film d'écran vis-à-vis de la lumière
US8552089B2 (en) 2009-04-27 2013-10-08 Dic Corporation Ink composition for forming light shielding film of organic semiconductor device, method for forming light shielding film, and organic transistor device having light shielding film

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