CA2661750C - Sheet-fed offset printing inks and varnishes comprising new solvents - Google Patents
Sheet-fed offset printing inks and varnishes comprising new solvents Download PDFInfo
- Publication number
- CA2661750C CA2661750C CA2661750A CA2661750A CA2661750C CA 2661750 C CA2661750 C CA 2661750C CA 2661750 A CA2661750 A CA 2661750A CA 2661750 A CA2661750 A CA 2661750A CA 2661750 C CA2661750 C CA 2661750C
- Authority
- CA
- Canada
- Prior art keywords
- offset printing
- monocarboxylic acid
- acid moieties
- saturated monocarboxylic
- triglyceride
- Prior art date
- Legal status (The legal status 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 status listed.)
- Active
Links
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
- C09D11/10—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
- C09D11/104—Polyesters
- C09D11/105—Alkyd resins
-
- 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
-
- 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
-
- 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
- C09D11/06—Printing inks based on fatty oils
Abstract
An offset printing varnish, comprising a solvent, is provided. The solvent com¬ prises at least one triglyceride with saturated monocarboxylic acid moieties, which solvent is preferably food safe.
Description
- 1 ¨
SHEET-FED OFFSET PRINTING INKS AND VARNISHES COMPRISING NEW
SOLVENTS
The present invention relates to novel low odour inks and varnishes useful for offset lithographic printing, especially sheet-fed offset lithographic printing.
Sheet-fed offset lithography is the dominant printing process for the printing of folding cartons for many purposes, including for use as food packaging. How-ever, where an ink is to be used on food packaging, it was hitherto essential, from the point of view of customer's acceptance, that it should not contaminate the food or impact any unnatural odour to it. Moreover, there is an increasing tendency for legislation to prescribe very low levels of contaminants in foods and other matter, which could affect public health. Contamination, in this context, can result from migration of public health affecting components of an ink into the food stuff or other packaged material or from undesirable odours imparted to the packaged material by the ink.
The development of printing inks which can be used for sheet-fed offset lithog-raphy and which allow little or no migration of their components whilst being essentially odourless or having little odour was therefore an aim of research.
One of the main odorous components of offset inks is the solvent used. It is in the nature of offset lithography, that the solvent must be organic and insoluble in water. Many solvents having these properties are not only highly odorous but also many of them are toxic to a greater or lesser extent. The choice of solvents for this purpose is, therefore, highly restricted.
In DE 196 53 828 C2 a low migration printing ink with little odour containing a ¨ 2 ¨
rosin modified phenolic resin and/or a maleic resin and/or a modified hydrocar-bon resin and/or a rosin ester is described, which contains fatty acid esters of polyvalent alcohols with high sterically required space.
The subject of WO 2005/090498 A1 are low migration, low odour inks or var-nishes, that comprise at least one water-insoluble ester of a polycarboxylic acid with an alcohol having at least 4 carbon atoms, also with high sterically required space.
The disclosure of WO 97/35934 is a vegetable-oil containing printing ink vehicle, which does not contain any volatile organic compound.
The approach to overcome the afore-mentioned problems according to the present invention is to use suited solvents that are food safe and hence do not show toxic or malodorous effects, so that their migration properties are not important for their use.
According to the prior art solvents for use in varnishes and respective sheet-fed offset printing are to be sterically hindered molecules which do not migrate, i.e.
which cannot contaminate packaged food because of being immobile. The used compounds are quite complex as to there chemical structure.
It is therefore a desire for providing solvents suited to be used in var-nishes/printing inks for offset printing, especially sheet-fed offset printing, com-prising compounds which are not restricted to the condition of being sterically hindered and which are, moreover, food safe.
This object is solved by the subject-matter claimed according to the present invention. It has surprisingly been found that a class of compounds, namely certain triglycerides based on saturated aliphatic monocarboxylic acids, are ¨ 3 ¨
useful as solvents for offset printing inks and varnishes, especially sheet-fed offset printing inks and varnishes and are capable to give a number of improve-ments over the known inks including equivalent or lower odour or equivalent or improved stability on the press, without requiring the property of low migration, since those compounds are food safe (see e. g. "N. Weber et al., UGB-Forum 4/2002, pages 183-186", "K. Mukherjee, ForschungsReport, 1/1998, pages 38-41").
Thus, the present invention consists of an offset printing ink or varnish, particu-larly useful in sheet-fed offset lithographic printing, characterised in that the solvent comprises at least one water-insoluble triglyceride with saturated mono-carboxylic acid moieties, preferably comprising from 5 to 22 carbon atoms.
The triglyceride as defined above is food safe, preferably the same applies to all components present in the solvent.
The term "food safe" means that the compound is health safe, not toxic and can be ingested without being detrimental to the human body.
The term "saturated monocarboxylic acid moiety", as defined herein, means a residue of the following type:
¨C(0)¨AlkYlsaturated, e. g. Acetyl (¨C(0)¨CH3) as a "saturated monocarboxylic acid moiety having two carbon atoms" or Capryl (¨C(0)¨C7H15) as a "saturated monocarboxylic acid moiety having eight carbon atoms".
When using compounds containing unsaturated acid moieties, the odour of the resulting inks and varnishes increases, which is not desirable.
Since the oxidative drying process and the by-products generated by it are an important source of odour development in finished prints, a careful selection of raw materials is necessary. According to a preferred embodiment of the inven-tion driers as well as raw materials with oxidative drying potential (as used in conventional sheet-fed offset printing inks) are absent from the composition.
Good rub resistance of the finished prints can be achieved by using the printing inks according to the present invention together with a water based overprint varnish (OPV).
The general composition of printing inks or varnishes for offset lithographic printing, including sheet-fed offset lithographic printing, is well known, and is described in considerable detail in, for example, "R. H. Leach et al., The Printing Ink Manual, 5th edition, 1993, pages 342-452" and in US Patents No 5,382,282, No. 5,725,646 and No. 6,489,375.
In general terms, a lithographic printing ink should have a low surface tension, be water-repellent, be capable of emulsifying with a fount solution, and, for conventional sheet-fed offset lithography, must be capable of drying without radiation. These very particular requirements are met by careful formulation and choice of the various components and are known in the printing ink industry.
The solvent used in the ink or varnish composition of the present invention comprises at least one water-insoluble triglyceride with saturated monocarbox-ylic acid moieties having from 6 to 22 carbon atoms. The corresponding mono-carboxylic acids are aliphatic and have only one carboxylic acid group which forms an ester group with glycerol.
The three acid residues bound via ester groups to the glycerol can be the same ¨ 5 ¨
or different.
Examples of aliphatic monocarboxylic acids include valeric acid (5 carbon at-oms), caproic acid (6 carbon atoms), oenanthic acid (7 carbon atoms), caprylic acid (8 carbon atoms), pelargonic acid (9 carbon atoms), capric acid (10 carbon atoms), lauric acid (12 carbon atoms), myristic acid (14 carbon atoms), palmitic acid (16 carbon atoms), stearic acid (18 carbon atoms), arachidic acid (20 car-bon atoms) and behenic acid (22 carbon atoms).
Preferably, the triglyceride is a so called MCT (medium chained triglyceride).
More preferably, the saturated monocarboxylic acid moieties each have inde-pendently 8 to 10 carbon atoms and most preferably 8 and/or 10 carbon atoms.
In the latter and the most preferred case, the inks or varnishes according to the present invention comprise solvents that comprise at least one of the following compounds:
SHEET-FED OFFSET PRINTING INKS AND VARNISHES COMPRISING NEW
SOLVENTS
The present invention relates to novel low odour inks and varnishes useful for offset lithographic printing, especially sheet-fed offset lithographic printing.
Sheet-fed offset lithography is the dominant printing process for the printing of folding cartons for many purposes, including for use as food packaging. How-ever, where an ink is to be used on food packaging, it was hitherto essential, from the point of view of customer's acceptance, that it should not contaminate the food or impact any unnatural odour to it. Moreover, there is an increasing tendency for legislation to prescribe very low levels of contaminants in foods and other matter, which could affect public health. Contamination, in this context, can result from migration of public health affecting components of an ink into the food stuff or other packaged material or from undesirable odours imparted to the packaged material by the ink.
The development of printing inks which can be used for sheet-fed offset lithog-raphy and which allow little or no migration of their components whilst being essentially odourless or having little odour was therefore an aim of research.
One of the main odorous components of offset inks is the solvent used. It is in the nature of offset lithography, that the solvent must be organic and insoluble in water. Many solvents having these properties are not only highly odorous but also many of them are toxic to a greater or lesser extent. The choice of solvents for this purpose is, therefore, highly restricted.
In DE 196 53 828 C2 a low migration printing ink with little odour containing a ¨ 2 ¨
rosin modified phenolic resin and/or a maleic resin and/or a modified hydrocar-bon resin and/or a rosin ester is described, which contains fatty acid esters of polyvalent alcohols with high sterically required space.
The subject of WO 2005/090498 A1 are low migration, low odour inks or var-nishes, that comprise at least one water-insoluble ester of a polycarboxylic acid with an alcohol having at least 4 carbon atoms, also with high sterically required space.
The disclosure of WO 97/35934 is a vegetable-oil containing printing ink vehicle, which does not contain any volatile organic compound.
The approach to overcome the afore-mentioned problems according to the present invention is to use suited solvents that are food safe and hence do not show toxic or malodorous effects, so that their migration properties are not important for their use.
According to the prior art solvents for use in varnishes and respective sheet-fed offset printing are to be sterically hindered molecules which do not migrate, i.e.
which cannot contaminate packaged food because of being immobile. The used compounds are quite complex as to there chemical structure.
It is therefore a desire for providing solvents suited to be used in var-nishes/printing inks for offset printing, especially sheet-fed offset printing, com-prising compounds which are not restricted to the condition of being sterically hindered and which are, moreover, food safe.
This object is solved by the subject-matter claimed according to the present invention. It has surprisingly been found that a class of compounds, namely certain triglycerides based on saturated aliphatic monocarboxylic acids, are ¨ 3 ¨
useful as solvents for offset printing inks and varnishes, especially sheet-fed offset printing inks and varnishes and are capable to give a number of improve-ments over the known inks including equivalent or lower odour or equivalent or improved stability on the press, without requiring the property of low migration, since those compounds are food safe (see e. g. "N. Weber et al., UGB-Forum 4/2002, pages 183-186", "K. Mukherjee, ForschungsReport, 1/1998, pages 38-41").
Thus, the present invention consists of an offset printing ink or varnish, particu-larly useful in sheet-fed offset lithographic printing, characterised in that the solvent comprises at least one water-insoluble triglyceride with saturated mono-carboxylic acid moieties, preferably comprising from 5 to 22 carbon atoms.
The triglyceride as defined above is food safe, preferably the same applies to all components present in the solvent.
The term "food safe" means that the compound is health safe, not toxic and can be ingested without being detrimental to the human body.
The term "saturated monocarboxylic acid moiety", as defined herein, means a residue of the following type:
¨C(0)¨AlkYlsaturated, e. g. Acetyl (¨C(0)¨CH3) as a "saturated monocarboxylic acid moiety having two carbon atoms" or Capryl (¨C(0)¨C7H15) as a "saturated monocarboxylic acid moiety having eight carbon atoms".
When using compounds containing unsaturated acid moieties, the odour of the resulting inks and varnishes increases, which is not desirable.
Since the oxidative drying process and the by-products generated by it are an important source of odour development in finished prints, a careful selection of raw materials is necessary. According to a preferred embodiment of the inven-tion driers as well as raw materials with oxidative drying potential (as used in conventional sheet-fed offset printing inks) are absent from the composition.
Good rub resistance of the finished prints can be achieved by using the printing inks according to the present invention together with a water based overprint varnish (OPV).
The general composition of printing inks or varnishes for offset lithographic printing, including sheet-fed offset lithographic printing, is well known, and is described in considerable detail in, for example, "R. H. Leach et al., The Printing Ink Manual, 5th edition, 1993, pages 342-452" and in US Patents No 5,382,282, No. 5,725,646 and No. 6,489,375.
In general terms, a lithographic printing ink should have a low surface tension, be water-repellent, be capable of emulsifying with a fount solution, and, for conventional sheet-fed offset lithography, must be capable of drying without radiation. These very particular requirements are met by careful formulation and choice of the various components and are known in the printing ink industry.
The solvent used in the ink or varnish composition of the present invention comprises at least one water-insoluble triglyceride with saturated monocarbox-ylic acid moieties having from 6 to 22 carbon atoms. The corresponding mono-carboxylic acids are aliphatic and have only one carboxylic acid group which forms an ester group with glycerol.
The three acid residues bound via ester groups to the glycerol can be the same ¨ 5 ¨
or different.
Examples of aliphatic monocarboxylic acids include valeric acid (5 carbon at-oms), caproic acid (6 carbon atoms), oenanthic acid (7 carbon atoms), caprylic acid (8 carbon atoms), pelargonic acid (9 carbon atoms), capric acid (10 carbon atoms), lauric acid (12 carbon atoms), myristic acid (14 carbon atoms), palmitic acid (16 carbon atoms), stearic acid (18 carbon atoms), arachidic acid (20 car-bon atoms) and behenic acid (22 carbon atoms).
Preferably, the triglyceride is a so called MCT (medium chained triglyceride).
More preferably, the saturated monocarboxylic acid moieties each have inde-pendently 8 to 10 carbon atoms and most preferably 8 and/or 10 carbon atoms.
In the latter and the most preferred case, the inks or varnishes according to the present invention comprise solvents that comprise at least one of the following compounds:
- 2,3-bis(octanyloxy)propyl octanoate - 2,3-bis(octanyloxy)propyl decanoate - 2-(decanyloxy)-3-(octanyloxy)propyl octanoate - 2-(decanyloxy)-3-(octanyloxy)propyl decanoate - 3-(decanyloxy)-2-(octanyloxy)propyl decanoate - 2,3-bis(decanyloxy)propyl decanoate Commercial examples for triglycerides or mixtures thereof that can be used in the present invention are CrodamolO GTCC by Croda, WitafrolO 7420 by HuIs AG, MyritolO 312 by Cognis, RotefanO GTCC by Ecogreen Oleochemicals or RaidiamulsO 2106 by Oleon.
Although the triglyceride may be used as the only solvent in the compositions according to the present invention, which is most preferred, also further suited solvents may be used, for example for achieving particular rheological proper-ties, provided that they are also food safe. A solvent other than a triglyceride may optionally be present in the compositions in a maximum amount of 60% by weight, based on the total amount of solvent used. More preferably, from 45%
to 90% by weight, still more preferably from 50% to 80%, and most preferably from 55% to 65% by weight of the solvent consists of the triglyceride.
In a special embodiment of the present invention the at least one triglyceride is the sole solvent.
Preferably the triglyceride solvent according to the present invention is present in a varnish in an amount of from 34 to 70% by weight, based on the total weight of the varnish, more preferably in an amount of from 38 to 60% by weight and most preferably in an amount of from 42 to 56% by weight.
In an especially preferred embodiment of the present invention the varnish comprises the following components (in (:)/0 by weight of the varnish):
Triglyceride with saturated monocarboxylic acid moieties 38-60 Alkyd resin 0-25 Ester of hydrogenated rosin 0-25 One or more phenolic modified rosin resins 0-45 One or more maleic resins 0-30 One or more phenolic free rosin resins 0-45 Gelling agent 0-2 Preferably the triglyceride solvent is present in an ink according to the present ¨ 7 ¨
invention in an amount of 30 to 45% by weight, more preferably in an amount of 32 to 43% by weight and most preferably in an amount of 34 to 41% by weight, based on the total weight of the printing ink composition.
The solvent, or mixture of solvents, used according to the present invention preferably has a melting point such that it is liquid at the temperature at which the printing ink or varnish is to be used. Hence, it should be liquid at the tem-perature of the printing press, and preferably even at ambient temperature, e.g.
at temperatures above 10 to 5 C. In some cases, for example if the printing ink or varnish is to be used only in warm atmospheres, it may be possible that the solvent is solid at the mentioned ambient temperatures, provided that it melts at a somewhat higher temperature, such as at 25 C.
The resin component in a lithographic prinitng ink composition or varnish func-tions, among other things, as a film former to bind the varnish and pigment together and, when the ink or varnish dries, to bind the same to the receiving substrate. The resin component also contributes to the properties of hardness, gloss, adhesion and flexibility of an ink and must be compatible with the solvent component of the varnish. In conventional oleoresinous systems, the resin conn-ponent commonly comprises a first or hard resin component and a second resin component which typically is an alkyd or polyester resin, but which can comprise various other compositions and resins as well.
Hard resins usable in the lithographic inks or varnishes of the present invention include, for example, natural or processed resins such as rosins, rosin esters, maleic modified resins, rosin modified fumaric resins, dimerized and polymer-ised rosins, phenolics, rosin modified phenolics, terpenes, polyamides, cyclised rubber, acrylics, hydrocarbons and modified hydrocarbons. Also included among the available resins are those identified in "The Printing Ink Manual', supra.
¨ 8 ¨
The lithographic inks of the present invention will usually include at least one pigment, the nature of which is not critical to the present invention, and which may be chosen from any of those pigments well known to those skilled in the art. Alternatively, the ink may include an extender. Varnishes will not normally include any pigment or extender in their composition.
Procedures To produce a test varnish, 2/3 of the capryl/caprate glycerine ester were added to a reaction vessel, stirred and heated to 180 C. Then possible other liquid components ¨ alkyd or hydrogenated rosin ester - and the hard resins were added, ensuring that the temperature did not fall below 160 C. The mix-ture was heated up to 180 C and held at that temperature for 60 minutes.
Then the remaining part of the ester solvent was added and the mixture was allowed to cool to 160 C. In case of a non gelled varnish the varnish is further cooled down to room temperature.
In case of a gelled varnish (example 3) the gelling agent was then added with quick stirring and the whole varnish was heated to 180 C and maintained at that temperature for 30 minutes. External cooling then reduced the temperature to 110 C and the varnish was discharged from the reaction vessel.
The inks were prepared using the following method. The pigment(s) and other solid components (except the polyethylene wax) were dispersed in the varnish and the mixture was thoroughly mixed with a triple roller mill. The poly-ethylene wax was then added and the mixture was again passed over the triple roller mill for de-aerating. The viscosity and tack were adjusted, prior to de-aerating, by addition of small amounts of the capryl/caprate glycerine ester, to give the final composition shown in Table 1.
Table 1 : Process Ink Set:
Trade Name Supplier Yellow Magenta Cyan Black Radiamuls 2106 Oleon 9,5 10,0 9,0 7,0 Varnish 3 Sun Chemical 66,7 61,7 65,2 49,0 Setalin V 414 Hexion 8,0 9,0 7,0 12,0 Zeolite Pulver 4A A+E Fischer 0,8 0,8 0,8 8,0 Superslip 6515XF Micro Powders 0,8 0,8 0,8 0,8 BHT Helm AG 0,2 0,2 0,2 0,2 Aluminum Silicate ASP 170 Engelhardt 3,0 Sunbrite Yellow 2125 Sun Chemical 11,0 Sym. Brill Carmin 613308 DIC 9,5 Sym. Brill Carmin 613303 DIC 8,0 1,0 Fastogen Blue 5375 SD DIC 17,0 2,0 Spezialruss 250 Degussa 20,0 100,0 100,0 100,0 100,0 Preparation of printed material Test prints were produced on a Heidelberg MO 4-colour press including a unit for application of water-based overprint varnishes. Press speed was be-tween 7000-9000 sheets/hour, using a fountain solution containing 6-9% by volume isopropanol. Printing was carried out with standard optical densities, yellow = 1.35, magenta = 1.50, cyan = 1.40 and black = 1.80, using Fuji plates and Astral Premium blankets. The substrate used was Invercote G, which is a standard substrate for packaging. Prints were produced using a water-based overprint varnish. Samples for analysis were wrapped in aluminium foil 24 hrs after printing.
Robinson test The odour and taint caused by the inks of the present invention were tested by the well known Robinson test.
This is a test originally devised by the Technical Committee of the Inter-national Office of Cocoa and Chocolate to determine whether odours from pack-aging materials are transferred to cocoa and chocolate products. It is now also used more generally to check on the odour and taint likely to transfer from pack-aging materials used in the food industry. The test was carried out as follows:
A petri dish containing about 25 g of fresh grated milk chocolate was placed in a clean 1 litre preserving jar. 16 representative round samples (9 cm diameter, total area of the 16 samples 1017 cm2) of the packaging material to be evaluated were placed in the jar, so that sample and chocolate were not in contact with one another. A jar, the "blank", in all respects similar, but without any sample and a jar with unprinted substrate were also prepared. The jars were closed with a lid. They were then stored for 24 hours in a dark, odourless place at 23 C. A panel of tasters then compared the odour and the flavour of the chocolate in each sample jar with the chocolate in the blank. The results were evaluated on the following scale:
0 = no difference in odour/flavour 1 = odour/flavour difference just perceptible 2 = noticeable change in odour/flavour 3 = significant change in odour/flavour 4 = intense change in odour/flavour Four-colour (black, cyan, magenta, yellow) prints were produced by print-ing as described above and were then tested. The sets of inks used were:
¨ 11 ¨
set A, standard offset inks, Irocart Process Inks, a set of currently available Sun Chemical conventional sheetfed offset inks containing driers;
set B, Irocart GN Low Hex ink, a set of currently available Sun Chemical con-ventional sheetfed offset inks formulated for low odour and low taint;
set C, the inks of table 1. The results are shown in Table 2 below.
Table 2 Sample Odour rating Taint rating Blank 0 0 Blank substrate 0.5 0 Set A 3.5 3.0 Set B 0.5 0.5 Set C 0.5 0.0 In the following examples the components (amounts in (:)/0 by weight) were mixed to form varnishes (Examples 1-5) or inks (Examples 6-7):
¨ 12 -Example 1: Varnish 1 Trade name Supplier Chemical description wt.-%
RofetanO GTCC Deutsche Hydrierwerke Capryl/caprate glycerine ester ForalynO D Eastmann Chemicals Hydrogenated rosin ester TergrafO 902 Cray Valley Phenolic modified rosin esters Example 2: Varnish 2 Trade name Supplier Chemical description wt.-%
RadiamulsO 2106 Oleon Capryl/caprate glycerine ester SetalinO V414 Hexion Coconutoil alkyd resin TergrafO 902 Cray Valley Phenolic modified rosin esters Example 3: Varnish 3 Trade name Supplier Chemical description wt.-%
RofetanO GTCC Deutsche Hydrierwerke Capryl/caprate glycerine ester 47.2 Setalin OV414 Hexion Coconutoil alkyd resin TergrafO 940 Cray Valley Phenolic modified rosin esters TergrafO ZU 80 Cray Valley Phenolic modified rosin esters Gelling agent 50408 Sun Chemical Gelling agent aluminum based 1,8 Example 4: Varnish 4 Trade name Supplier Chemical description wt.-%
RofetanO GTCC Deutsche Hydrierwerke Capryl/caprate glycerine ester SetalinO V414 Hexion Coconutoil alkyd resin TergrafO 902 Cray Valley Phenolic modified rosin esters TergrafO 940 Cray Valley Phenolic modified rosin esters Example 5: Varnish 5 Trade name Supplier Chemical description wt.-%
RofetanO GTCC Deutsche Hydrierwerke Capryl/caprate glycerine ester 54 ForalynO D Eastmann Chemicals Hydrogenated rosin ester Te rg ref 902 Cray Valley Phenolic modified rosin esters 18 Te rg ref 940 Cray Valley Phenolic modified rosin esters 18 Example 6: Ink 1 Trade name Supplier Chemical description wt.-%
Varnish 2 Sun Chemical Varnish 67.5 BHT Helm AG BHT
0.1 Setalin V414 Hexion Coconutoil alkyd resin Zeolithe powder 4A A+E Fischer Na-Al-Silicate 0.6 Superslip 6515XF Micro Powders Micronized polyamide wax 0.8 Symuler Brilliant Carmin 6B 308 DIC Pigment Red 57:1 9.5 Symuler Brilliant Carmin 6B 303 DIC Pigment Red 57:1 RofetanO Ecogreen Triglyceride with saturated-5.5 monocarboxylic acid moieties Example 7: Ink 2 Trade name Supplier Chemical description wt.-%
Varnish 3 Sun Chemical Varnish 66.5 BHT Helm AG BHT
0.1 Setalin V414 Hexion Coconutoil alkyd resin Zeolithe powder 4A A+E Fischer Na-Al-Silicate 0.6 Superslip 6515XF Micro Powders Micronized polyamide wax 0.8 Symuler Brilliant Carmin 6B 308 DIC Pigment Red 57:1 9.5 Symuler Brilliant Carmin 6B 303 DIC Pigment Red 57:1 RadiamulsO 2106 Oleon Triglyceride with saturated-6.5 monocarboxylic acid moieties
Although the triglyceride may be used as the only solvent in the compositions according to the present invention, which is most preferred, also further suited solvents may be used, for example for achieving particular rheological proper-ties, provided that they are also food safe. A solvent other than a triglyceride may optionally be present in the compositions in a maximum amount of 60% by weight, based on the total amount of solvent used. More preferably, from 45%
to 90% by weight, still more preferably from 50% to 80%, and most preferably from 55% to 65% by weight of the solvent consists of the triglyceride.
In a special embodiment of the present invention the at least one triglyceride is the sole solvent.
Preferably the triglyceride solvent according to the present invention is present in a varnish in an amount of from 34 to 70% by weight, based on the total weight of the varnish, more preferably in an amount of from 38 to 60% by weight and most preferably in an amount of from 42 to 56% by weight.
In an especially preferred embodiment of the present invention the varnish comprises the following components (in (:)/0 by weight of the varnish):
Triglyceride with saturated monocarboxylic acid moieties 38-60 Alkyd resin 0-25 Ester of hydrogenated rosin 0-25 One or more phenolic modified rosin resins 0-45 One or more maleic resins 0-30 One or more phenolic free rosin resins 0-45 Gelling agent 0-2 Preferably the triglyceride solvent is present in an ink according to the present ¨ 7 ¨
invention in an amount of 30 to 45% by weight, more preferably in an amount of 32 to 43% by weight and most preferably in an amount of 34 to 41% by weight, based on the total weight of the printing ink composition.
The solvent, or mixture of solvents, used according to the present invention preferably has a melting point such that it is liquid at the temperature at which the printing ink or varnish is to be used. Hence, it should be liquid at the tem-perature of the printing press, and preferably even at ambient temperature, e.g.
at temperatures above 10 to 5 C. In some cases, for example if the printing ink or varnish is to be used only in warm atmospheres, it may be possible that the solvent is solid at the mentioned ambient temperatures, provided that it melts at a somewhat higher temperature, such as at 25 C.
The resin component in a lithographic prinitng ink composition or varnish func-tions, among other things, as a film former to bind the varnish and pigment together and, when the ink or varnish dries, to bind the same to the receiving substrate. The resin component also contributes to the properties of hardness, gloss, adhesion and flexibility of an ink and must be compatible with the solvent component of the varnish. In conventional oleoresinous systems, the resin conn-ponent commonly comprises a first or hard resin component and a second resin component which typically is an alkyd or polyester resin, but which can comprise various other compositions and resins as well.
Hard resins usable in the lithographic inks or varnishes of the present invention include, for example, natural or processed resins such as rosins, rosin esters, maleic modified resins, rosin modified fumaric resins, dimerized and polymer-ised rosins, phenolics, rosin modified phenolics, terpenes, polyamides, cyclised rubber, acrylics, hydrocarbons and modified hydrocarbons. Also included among the available resins are those identified in "The Printing Ink Manual', supra.
¨ 8 ¨
The lithographic inks of the present invention will usually include at least one pigment, the nature of which is not critical to the present invention, and which may be chosen from any of those pigments well known to those skilled in the art. Alternatively, the ink may include an extender. Varnishes will not normally include any pigment or extender in their composition.
Procedures To produce a test varnish, 2/3 of the capryl/caprate glycerine ester were added to a reaction vessel, stirred and heated to 180 C. Then possible other liquid components ¨ alkyd or hydrogenated rosin ester - and the hard resins were added, ensuring that the temperature did not fall below 160 C. The mix-ture was heated up to 180 C and held at that temperature for 60 minutes.
Then the remaining part of the ester solvent was added and the mixture was allowed to cool to 160 C. In case of a non gelled varnish the varnish is further cooled down to room temperature.
In case of a gelled varnish (example 3) the gelling agent was then added with quick stirring and the whole varnish was heated to 180 C and maintained at that temperature for 30 minutes. External cooling then reduced the temperature to 110 C and the varnish was discharged from the reaction vessel.
The inks were prepared using the following method. The pigment(s) and other solid components (except the polyethylene wax) were dispersed in the varnish and the mixture was thoroughly mixed with a triple roller mill. The poly-ethylene wax was then added and the mixture was again passed over the triple roller mill for de-aerating. The viscosity and tack were adjusted, prior to de-aerating, by addition of small amounts of the capryl/caprate glycerine ester, to give the final composition shown in Table 1.
Table 1 : Process Ink Set:
Trade Name Supplier Yellow Magenta Cyan Black Radiamuls 2106 Oleon 9,5 10,0 9,0 7,0 Varnish 3 Sun Chemical 66,7 61,7 65,2 49,0 Setalin V 414 Hexion 8,0 9,0 7,0 12,0 Zeolite Pulver 4A A+E Fischer 0,8 0,8 0,8 8,0 Superslip 6515XF Micro Powders 0,8 0,8 0,8 0,8 BHT Helm AG 0,2 0,2 0,2 0,2 Aluminum Silicate ASP 170 Engelhardt 3,0 Sunbrite Yellow 2125 Sun Chemical 11,0 Sym. Brill Carmin 613308 DIC 9,5 Sym. Brill Carmin 613303 DIC 8,0 1,0 Fastogen Blue 5375 SD DIC 17,0 2,0 Spezialruss 250 Degussa 20,0 100,0 100,0 100,0 100,0 Preparation of printed material Test prints were produced on a Heidelberg MO 4-colour press including a unit for application of water-based overprint varnishes. Press speed was be-tween 7000-9000 sheets/hour, using a fountain solution containing 6-9% by volume isopropanol. Printing was carried out with standard optical densities, yellow = 1.35, magenta = 1.50, cyan = 1.40 and black = 1.80, using Fuji plates and Astral Premium blankets. The substrate used was Invercote G, which is a standard substrate for packaging. Prints were produced using a water-based overprint varnish. Samples for analysis were wrapped in aluminium foil 24 hrs after printing.
Robinson test The odour and taint caused by the inks of the present invention were tested by the well known Robinson test.
This is a test originally devised by the Technical Committee of the Inter-national Office of Cocoa and Chocolate to determine whether odours from pack-aging materials are transferred to cocoa and chocolate products. It is now also used more generally to check on the odour and taint likely to transfer from pack-aging materials used in the food industry. The test was carried out as follows:
A petri dish containing about 25 g of fresh grated milk chocolate was placed in a clean 1 litre preserving jar. 16 representative round samples (9 cm diameter, total area of the 16 samples 1017 cm2) of the packaging material to be evaluated were placed in the jar, so that sample and chocolate were not in contact with one another. A jar, the "blank", in all respects similar, but without any sample and a jar with unprinted substrate were also prepared. The jars were closed with a lid. They were then stored for 24 hours in a dark, odourless place at 23 C. A panel of tasters then compared the odour and the flavour of the chocolate in each sample jar with the chocolate in the blank. The results were evaluated on the following scale:
0 = no difference in odour/flavour 1 = odour/flavour difference just perceptible 2 = noticeable change in odour/flavour 3 = significant change in odour/flavour 4 = intense change in odour/flavour Four-colour (black, cyan, magenta, yellow) prints were produced by print-ing as described above and were then tested. The sets of inks used were:
¨ 11 ¨
set A, standard offset inks, Irocart Process Inks, a set of currently available Sun Chemical conventional sheetfed offset inks containing driers;
set B, Irocart GN Low Hex ink, a set of currently available Sun Chemical con-ventional sheetfed offset inks formulated for low odour and low taint;
set C, the inks of table 1. The results are shown in Table 2 below.
Table 2 Sample Odour rating Taint rating Blank 0 0 Blank substrate 0.5 0 Set A 3.5 3.0 Set B 0.5 0.5 Set C 0.5 0.0 In the following examples the components (amounts in (:)/0 by weight) were mixed to form varnishes (Examples 1-5) or inks (Examples 6-7):
¨ 12 -Example 1: Varnish 1 Trade name Supplier Chemical description wt.-%
RofetanO GTCC Deutsche Hydrierwerke Capryl/caprate glycerine ester ForalynO D Eastmann Chemicals Hydrogenated rosin ester TergrafO 902 Cray Valley Phenolic modified rosin esters Example 2: Varnish 2 Trade name Supplier Chemical description wt.-%
RadiamulsO 2106 Oleon Capryl/caprate glycerine ester SetalinO V414 Hexion Coconutoil alkyd resin TergrafO 902 Cray Valley Phenolic modified rosin esters Example 3: Varnish 3 Trade name Supplier Chemical description wt.-%
RofetanO GTCC Deutsche Hydrierwerke Capryl/caprate glycerine ester 47.2 Setalin OV414 Hexion Coconutoil alkyd resin TergrafO 940 Cray Valley Phenolic modified rosin esters TergrafO ZU 80 Cray Valley Phenolic modified rosin esters Gelling agent 50408 Sun Chemical Gelling agent aluminum based 1,8 Example 4: Varnish 4 Trade name Supplier Chemical description wt.-%
RofetanO GTCC Deutsche Hydrierwerke Capryl/caprate glycerine ester SetalinO V414 Hexion Coconutoil alkyd resin TergrafO 902 Cray Valley Phenolic modified rosin esters TergrafO 940 Cray Valley Phenolic modified rosin esters Example 5: Varnish 5 Trade name Supplier Chemical description wt.-%
RofetanO GTCC Deutsche Hydrierwerke Capryl/caprate glycerine ester 54 ForalynO D Eastmann Chemicals Hydrogenated rosin ester Te rg ref 902 Cray Valley Phenolic modified rosin esters 18 Te rg ref 940 Cray Valley Phenolic modified rosin esters 18 Example 6: Ink 1 Trade name Supplier Chemical description wt.-%
Varnish 2 Sun Chemical Varnish 67.5 BHT Helm AG BHT
0.1 Setalin V414 Hexion Coconutoil alkyd resin Zeolithe powder 4A A+E Fischer Na-Al-Silicate 0.6 Superslip 6515XF Micro Powders Micronized polyamide wax 0.8 Symuler Brilliant Carmin 6B 308 DIC Pigment Red 57:1 9.5 Symuler Brilliant Carmin 6B 303 DIC Pigment Red 57:1 RofetanO Ecogreen Triglyceride with saturated-5.5 monocarboxylic acid moieties Example 7: Ink 2 Trade name Supplier Chemical description wt.-%
Varnish 3 Sun Chemical Varnish 66.5 BHT Helm AG BHT
0.1 Setalin V414 Hexion Coconutoil alkyd resin Zeolithe powder 4A A+E Fischer Na-Al-Silicate 0.6 Superslip 6515XF Micro Powders Micronized polyamide wax 0.8 Symuler Brilliant Carmin 6B 308 DIC Pigment Red 57:1 9.5 Symuler Brilliant Carmin 6B 303 DIC Pigment Red 57:1 RadiamulsO 2106 Oleon Triglyceride with saturated-6.5 monocarboxylic acid moieties
Claims (19)
1. An offset printing varnish comprising a solvent, the solvent consisting of food safe components including at least one triglyceride with saturated monocarboxylic acid moieties.
2. The offset printing varnish according to claim 1, which is a sheet-fed offset printing varnish.
3. The offset printing varnish according to claim 1 or 2, wherein the saturated monocarboxylic acid moieties each comprise, independently, from 5 to 22 carbon atoms.
4. The offset printing varnish according to any one of claims 1-3, wherein the saturated monocarboxylic acid moieties each have, independently, 8 to 10 carbon atoms.
5. The offset printing varnish according to any one of claims 1-4, wherein the saturated monocarboxylic acid moieties each have, independently, 8 and/or 10 carbon atoms.
6. The offset printing varnish according to any one of claims 1-5, comprising from 34% to 70% by weight of the triglyceride with saturated monocarboxylic acid moieties.
7. The offset printing varnish according to any one of claims 1-6, comprising from 38% to 60% by weight of the triglyceride with saturated monocarboxylic acid moieties.
8. The offset printing varnish according to any one of claims 1-7, comprising from 42% to 56% by weight of the triglyceride with saturated monocarboxylic acid moieties.
9. The offset printing varnish according to any one of claims 1-8, comprising the following components (in % by weight):
triglyceride with saturated monocarboxylic acid moieties 38-60 alkyd resin 0-25 ester of hydrogenated rosin 0-25 one or more phenolic modified rosin resins 0-45 one or more maleic resins 0-30 one or more phenolic free rosin resins 0-45 gelling agent 0-2 .
triglyceride with saturated monocarboxylic acid moieties 38-60 alkyd resin 0-25 ester of hydrogenated rosin 0-25 one or more phenolic modified rosin resins 0-45 one or more maleic resins 0-30 one or more phenolic free rosin resins 0-45 gelling agent 0-2 .
10. An offset printing ink comprising a solvent, the solvent consisting of food safe components including at least one triglyceride with saturated monocarboxylic acid moieties.
11. The offset printing ink according to claim 10, which is a sheet-fed offset printing ink.
12. The offset printing ink according to claim 10 or 11, wherein the saturated monocarboxylic acid moieties each have, independently, from 5 to 22 carbon atoms.
13. The offset printing ink according to any one of claims 10-12, wherein the saturated monocarboxylic acid moieties each have, independently, 8 to 10 carbon atoms.
14. The offset printing ink according to any one of claims 10-13, wherein the saturated monocarboxylic acid moieties each have, independently, 8 and/or 10 carbon atoms.
15. The offset printing ink according to any one of claims 10-14, comprising from 30% to 45% by weight of the triglyceride with saturated monocarboxylic acid moieties.
16. The offset printing ink according to any one of claims 10-15, comprising from 32% to 43% by weight of the triglyceride with saturated monocarboxylic acid moieties.
17. The offset printing ink according to any one of claims 10-16, comprising from 34% to 41% by weight of the triglyceride with saturated monocarboxylic acid moieties.
18. A method for preparing a sheet-fed printing varnish comprising a solvent, the solvent consisting of food safe components including at least one triglyceride with saturated monocarboxylic acid moieties, the method comprising mixing at least one triglyceride with saturated monocarboxylic acid moieties with at least one hard resin usable in lithographic varnishes.
19. A method for preparing a sheet-fed printing ink comprising a sheet-fed printing varnish comprising a solvent, the solvent consisting of food safe components including at least one triglyceride with saturated monocarboxylic acid moieties, the method comprising mixing at least one varnish according to any one of claims 1-9 with other ingredients usable in lithographic printing inks.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US84024306P | 2006-08-25 | 2006-08-25 | |
| US60/840,243 | 2006-08-25 | ||
| PCT/US2007/076751 WO2008024968A1 (en) | 2006-08-25 | 2007-08-24 | Sheet-fed offset printing inks and varnishes comprising new solvents |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2661750A1 CA2661750A1 (en) | 2008-02-28 |
| CA2661750C true CA2661750C (en) | 2015-01-06 |
Family
ID=38710527
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2661750A Active CA2661750C (en) | 2006-08-25 | 2007-08-24 | Sheet-fed offset printing inks and varnishes comprising new solvents |
Country Status (10)
| Country | Link |
|---|---|
| US (3) | US8168708B2 (en) |
| EP (3) | EP2177579A1 (en) |
| AT (1) | ATE515543T1 (en) |
| CA (1) | CA2661750C (en) |
| DE (1) | DE202007018757U1 (en) |
| DK (1) | DK2054480T4 (en) |
| ES (1) | ES2369428T5 (en) |
| PL (1) | PL2054480T5 (en) |
| PT (1) | PT2054480E (en) |
| WO (1) | WO2008024968A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007012264A1 (en) | 2007-03-06 | 2008-09-11 | Epple Druckfarben Ag | Printing ink or printing varnish for food packaging |
| DE102007021134A1 (en) * | 2007-05-03 | 2008-11-06 | Cognis Ip Management Gmbh | Complex ester as solvent for printing inks (I) |
| DE102007021131A1 (en) * | 2007-05-03 | 2008-11-06 | Cognis Ip Management Gmbh | Complex ester as a solvent for printing inks (II) |
| WO2012154909A2 (en) | 2011-05-10 | 2012-11-15 | Sun Chemical Corporation | Cold foil adhesives used in food & non food packaging applications |
| DE102012103825A1 (en) * | 2012-05-02 | 2013-11-07 | Epple Druckfarben Ag | Offset printing ink or offset printing ink |
| IT201700012056A1 (en) * | 2017-02-03 | 2018-08-03 | Serio Martino Di | Compositions containing fatty acid esters of vegetable origin as solvents |
Family Cites Families (30)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2389781A (en) * | 1942-06-22 | 1945-11-27 | Gen Luminescent Corp | Luminescent coating material |
| US3665060A (en) * | 1969-11-17 | 1972-05-23 | Monsanto Co | Resin blend containing ethylene/vinyl chloride interpolymer |
| DE2118785A1 (en) * | 1971-04-14 | 1972-10-19 | Hebenbrock, Bernd, 1000 Berlin | Imitation water-marks on paper - by applying a linseed oil lacquer -water mixt or glycerin ester based mixt to engraved mark |
| DE3243532A1 (en) * | 1982-11-25 | 1984-05-30 | Basf Farben + Fasern Ag, 2000 Hamburg | PRINT INK |
| US5122188A (en) | 1990-05-03 | 1992-06-16 | The United States Of America, As Represented By The Secretary Of Agriculture | Vegetable oil-based printing ink |
| US5308390A (en) | 1992-09-17 | 1994-05-03 | Deluxe Corporation | Ink composition and method of making and using such composition |
| US5507864A (en) | 1994-11-14 | 1996-04-16 | Tektronix, Inc. | Phase change ink composition employing a combination of dyes |
| DE69601706T2 (en) | 1995-05-04 | 1999-10-14 | Coates Lorilleux S A | PRINT INK |
| DE19516028A1 (en) | 1995-05-04 | 1996-11-07 | Henkel Kgaa | Aromatic-free solvents for printing inks |
| JP3642358B2 (en) | 1995-12-06 | 2005-04-27 | 東洋紡績株式会社 | Polyester resin aqueous dispersion and process for producing the same |
| US5725646A (en) | 1996-03-13 | 1998-03-10 | Sun Chemical Corporation | Water-based offset lithographic printing ink |
| US5713990A (en) | 1996-03-27 | 1998-02-03 | The United States Of America As Represented By The Secretary Of Agriculture | Vegetable oil-based offset printing inks |
| DE19653828C5 (en) | 1996-12-21 | 2010-01-21 | Michael Huber München Gmbh | Migration, odor and swelling poor sheetfed offset printing ink |
| JP3686743B2 (en) * | 1997-06-16 | 2005-08-24 | 三菱製紙株式会社 | Developer ink and carbonless pressure-sensitive copying paper using the same |
| US6489375B2 (en) | 1998-07-07 | 2002-12-03 | Sun Chemical Corporation | Low VOC cationic curable lithographic printing inks |
| JP4093656B2 (en) | 1998-11-27 | 2008-06-04 | ハリマ化成株式会社 | Resin for printing ink |
| DE19910870C1 (en) * | 1999-03-11 | 2001-03-01 | Schwan Stabilo Cosmetics Gmbh | Pigment-based oil-based gel mass |
| US6284720B1 (en) * | 1999-09-03 | 2001-09-04 | Vertec Biosolvents, Llc | Environmentally friendly ink cleaning preparation |
| JP4390997B2 (en) | 2000-10-12 | 2009-12-24 | サカタインクス株式会社 | Ink composition for offset printing |
| JP2003064284A (en) * | 2001-08-30 | 2003-03-05 | Koyo Kagaku Kogyo Kk | Composition for printing ink washing |
| FR2829924B1 (en) * | 2001-09-21 | 2004-08-06 | Oreal | COSMETIC COMPOSITION FOR CARE OR MAKE-UP FOR KERATIN MATERIALS COMPRISING AN ALIPHATIC ESTER OF ESTER AND AN OIL WITH A MOLAR WEIGHT FROM 650 TO 10,000 G/MOL |
| DE10209013A1 (en) | 2002-02-25 | 2003-10-23 | Carl Epple Druckfarbenfabrik G | Offset printing ink and method for producing an offset printing ink |
| US8138250B2 (en) * | 2002-05-03 | 2012-03-20 | H R D Corporation | Wax for reducing mar and abrasion in inks and coatings |
| CA2489513C (en) | 2002-06-26 | 2011-05-24 | Mars, Incorporated | Edible inks for ink-jet printing on edible substrates |
| US6932465B2 (en) * | 2002-09-17 | 2005-08-23 | Canon Kabushiki Kaisha | Reaction solution, set of reaction solution and ink, ink jet recording apparatus and image recording method |
| MXPA05002860A (en) * | 2002-09-26 | 2005-05-27 | Ciba Sc Holding Ag | Pigment compositions for oil-based lithographic printing inks. |
| JP2004307555A (en) | 2003-04-02 | 2004-11-04 | Tohoku Ricoh Co Ltd | W/o type emulsion ink for stencil printing |
| CA2542876C (en) | 2003-10-27 | 2012-02-07 | Hrd Corp. | Novel wax for reducing mar and abrasion in inks and coatings |
| US20080282931A1 (en) | 2003-11-11 | 2008-11-20 | Stuart Cook Niven | Pigment Compositions for Oil-Based Lithographic Printing Ink System |
| GB2411900A (en) | 2004-03-12 | 2005-09-14 | Sun Chemical Bv | Low migration, low odour offset inks or varnishes |
-
2007
- 2007-08-24 PT PT07814426T patent/PT2054480E/en unknown
- 2007-08-24 CA CA2661750A patent/CA2661750C/en active Active
- 2007-08-24 EP EP09180011A patent/EP2177579A1/en not_active Withdrawn
- 2007-08-24 WO PCT/US2007/076751 patent/WO2008024968A1/en active Application Filing
- 2007-08-24 EP EP09179995A patent/EP2177578A1/en not_active Withdrawn
- 2007-08-24 DK DK07814426.8T patent/DK2054480T4/en active
- 2007-08-24 AT AT07814426T patent/ATE515543T1/en active
- 2007-08-24 PL PL07814426T patent/PL2054480T5/en unknown
- 2007-08-24 EP EP07814426.8A patent/EP2054480B2/en active Active
- 2007-08-24 ES ES07814426.8T patent/ES2369428T5/en active Active
- 2007-08-24 US US12/438,610 patent/US8168708B2/en active Active
- 2007-08-24 DE DE202007018757U patent/DE202007018757U1/en not_active Expired - Lifetime
-
2012
- 2012-03-09 US US13/416,789 patent/US8657945B2/en active Active
-
2014
- 2014-01-10 US US14/152,117 patent/US9546290B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| EP2177579A1 (en) | 2010-04-21 |
| EP2054480B2 (en) | 2014-08-20 |
| US20100174020A1 (en) | 2010-07-08 |
| ES2369428T9 (en) | 2012-04-04 |
| US9546290B2 (en) | 2017-01-17 |
| PL2054480T3 (en) | 2011-12-30 |
| DE202007018757U1 (en) | 2009-04-02 |
| DK2054480T3 (en) | 2012-04-16 |
| EP2177578A1 (en) | 2010-04-21 |
| EP2054480A1 (en) | 2009-05-06 |
| US20140128524A1 (en) | 2014-05-08 |
| PL2054480T5 (en) | 2015-05-29 |
| WO2008024968A1 (en) | 2008-02-28 |
| EP2054480B1 (en) | 2011-07-06 |
| US8168708B2 (en) | 2012-05-01 |
| DK2054480T4 (en) | 2014-11-24 |
| PT2054480E (en) | 2011-10-11 |
| ATE515543T1 (en) | 2011-07-15 |
| US8657945B2 (en) | 2014-02-25 |
| EP2054480B9 (en) | 2012-02-15 |
| US20120167798A1 (en) | 2012-07-05 |
| ES2369428T3 (en) | 2011-11-30 |
| ES2369428T5 (en) | 2014-10-15 |
| CA2661750A1 (en) | 2008-02-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9546290B2 (en) | Sheet-fed offset printing inks and varnishes comprising new solvents | |
| US5178672A (en) | Printing compositions | |
| EP1732995B1 (en) | Low migration, low odour offset inks or varnishes | |
| Bhattacharjee et al. | Development of Karanja oil based offset printing ink in comparison with Linseed oil | |
| US20120318158A1 (en) | Biodegradable vehicle/carrier for printing ink | |
| JP4522094B2 (en) | Waterless water-washable offset printing ink and method for producing the same | |
| EP3036295B1 (en) | Offset printing inks comprising an isosorbide fatty acid ester solvent | |
| JP4225073B2 (en) | Printing ink composition | |
| JP5155978B2 (en) | Offset printing ink composition and printed matter | |
| MXPA06010393A (en) | Low migration, low odour offset inks or varnishes | |
| CA1260172A (en) | Rapidly absorbed printing inks and their use | |
| EP1911811A1 (en) | Method for production of pigment composition, method for production of printing ink, and printed matter |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request |