CA1251881A - Lithographic water based fountain solution concentrates - Google Patents
Lithographic water based fountain solution concentratesInfo
- Publication number
- CA1251881A CA1251881A CA000441981A CA441981A CA1251881A CA 1251881 A CA1251881 A CA 1251881A CA 000441981 A CA000441981 A CA 000441981A CA 441981 A CA441981 A CA 441981A CA 1251881 A CA1251881 A CA 1251881A
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- Prior art keywords
- fountain solution
- buffer
- concentrate
- water
- newton
- 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.)
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41N—PRINTING PLATES OR FOILS; MATERIALS FOR SURFACES USED IN PRINTING MACHINES FOR PRINTING, INKING, DAMPING, OR THE LIKE; PREPARING SUCH SURFACES FOR USE AND CONSERVING THEM
- B41N3/00—Preparing for use and conserving printing surfaces
- B41N3/08—Damping; Neutralising or similar differentiation treatments for lithographic printing formes; Gumming or finishing solutions, fountain solutions, correction or deletion fluids, or on-press development
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- Printing Plates And Materials Therefor (AREA)
- Detergent Compositions (AREA)
Abstract
Abstract Lithographic Water Based Fountain Solution Concentrates Lithographic fountain solution concentrates which are combined with water to form improved fountain solutions. The concentrates contain specific quantities of buffer salts resulting in improved printing process characteristics. The buffer salts are the salts of polycarboxylic acids and organic bases such as amines. The use of alcohol in the fountain solutions is eliminated or substantially reduced.
Description
Description ~ithographic ~ater Based Fountain Solution Concentrates Technical Field This invention relates to water based concentrates which are mixed with water to form lithographic fountain solutions.
Background Art The web offset and lithographic printing processes employ planographic plates which transfer ink to a blanket roll which, in turn, then transfers the ink to a substrate thereby forming the printed images. The plates are referred to as planographic since the image and non-image areas are in the same plane. The plates are constructed so that with proper treatment the image areas are hydrophobic and oleophilic and thereby receptive to inks. The non-image areas are hydrophilic and are water receptive. In order to maintain the hydrophilic characteristics of the non-image areas, and to prevent ink from accumulating on the non-image areas, it is necessary to continuously treat the plate with a water based fountain solution. The water based fountain solution can be applied to the plate with a separate roll prior to inking, or, the in]s and fountain solution can be applied simultaneously as in the Dahlgren type of system.
Although plain tap water can be used as a fountain solution, it is known in the art to include additional ingredients in combination with water as a fountain ~2~
solution in order to improve the printing characteristics. It is known to include low boiling point alcohols, such as isopropanol and ethanol, and various surfactants to reduce surface tension and permit better wetting of the plates. It is also known to include an acid or a buffer to achieve a pH range of 4.0 - 6Ø Polyols such as glycerine are introduced into a fountain solution to act as a humectant and lubricant, and to assist in maintaining a thin layer of water on the hydrophilic areas of the plate. Biocides such as bactericides and algicides are added to control microbiological growth in the fountain solution.
Typically, fountain solutions are prepared at the printing site by mixing fountain concentrates with tap water.
The use of fountain solutions has been found to have numerous beneficial effects upon the printing process including reduction of water ink emulsion, reduced scumming, reduced paper defibration, reduced paper breakage, accelerated drying, longer press runs, - etc.
A typical fountain solution known in the art contains ethyl alcohol or isopropyl alcohol, glycerine, surfactant, bactericide or algicide, various amounts of an acidifying agent such as phosphoric acid, and water.
U.S. Patent 4,247,328 to Lawson et al discloses lithographic fountain concentrates containing a desensitizing material. The preferred desensitizing materials disclosed are salts of acids such as citric acid, phosphoric acid, tartaric acid and EDTA. Lawson states that although acids can be used as a :L2~
desensiti~er, salts are preferred since they act as buffers to overcome the use of acidic or alkaline tap waters. Lawson requires the use of at least 50%
organic sol~ent in the fountain solution concentrate.
U.S. Patent 4,150,996 discloses a fountain solution concentrate containing sulfanilic acid, formaldehyde, sodium hydroxide, and gum arabic. Gum arabic has been found to have numerous negative effects including gumming and glazing of plates and rollers and promotion of the growth of bacteria and algae.
U.S. Patent 4,278,467 to Fadner discloses a fountain solution which contains a substitutive replacement for isopropyl alcohol.
U.S. Patent 4,116,896 to Garret et al discloses a fountain solution whereby detrimental precipitation is controlled in acidic alcohol/water fountain solutions by the use of a chelating agent.
Accordingly, what is needed in the art is an improved fountain solution with a strong buffering capacity which will maintain a given pH range over time duriog the printing process thereby resulting in improvements in said printing process. Additionally, the improved fountain solution should eliminate alcohol or contain drastically reduced quantities of alcohol.
Disclosure of Invention It has now been found that by formulating a fountain solution concentrate having a strong buffer formed by reacting a polycarboxylic acid with an organic base and mixing about 1.0 wt.% to 6.0 wt.~ of said concentrate with water, a fountain solution exhibiting a superior buffering effect and containing no alcohol or extremely small quanti-ties of alcohol is obtained. The result-ant fountain solution formed from a concentrate when used with a lithographic printing press results in the following unexpected and surprising improvements: longer press run, decreased scumming, decreased ink/water emulsification, decreased linting and difibra-tion, deereased substrate breakage, improved drying, decreased strike-in, and improved ink/water balance.
This invention relates to concentrates for use in litho-graphic fountain solutions. The concentrates are a bleildof abuffer, a hygroscopic product, such as a polyol, water, and prefer-ably an alcohol. The concentrates used on lithographic presses '- using a Dahlgren dampening system do not contain alcohol. The concentrates of this invention can additionally contain a bacter-icide or algicide, and surfactants. The concentrate is blended with tap water to form a fountain solution sueh that the eoncent-rate comprises 1% to 6% of the fountain solution. The buffers used in this invention are the salts of polycarboxylic acids and organic bases (amines). The polycarboxylic acids have a PKa between 3 and 6 while the bases must have a PKb between 2 and 9. The polycarboxy-lic acids may have at least one hydroxyl group.
Detailed Description of the Invention The presen-t invention is directed to a water base concent-rate for use in lithographic fountain solutions, wherein said con-centrate is mixed in an amount of about 1.0 wt.% to 6.0 wt.% with water to form a fountain 8~
solution, said fountain solution concentrate characterized by:
water;
a buffer salt, comprising the salt of polycarboxylic acid having a PKa between 3 and 6 and an organic base having a PKb between 2 and 9;
low molecular weight alcohols;
an hygroscopic product such as glycerine or an equivalent polyol such as a polysaccharide or one of its derivatives (for example carboxymethylcellulose) or a product resulting from the polymerisation of the vinylpyrrodone, or a colloidal silicic acid;
and various optional ingredients such as surfactants, bactericides and/or algicides;
wherein said fountain solution made by mixing the concentrate with water, has - a pH between about 4~7 and about 5.3, - a surface tension between about 32 x 10-3 Newton/m and about 52 x 10-3 Newton/m.
The surface tension is adjusted according to the type of dampening system. For classic dampening systems (water based systems) the surface tension will be selected preferably between about 44 and 52 x 10~3 Newton/m. For alcohol dampening systems, the surface tension will be preferably between about 32 and 37 x 10~3 Newton/m; in this case, by selecting the proper fountain additi~e, it will be possible to decrease or suppress the alcohol usually used in that dampening system. If it is necessary the surface tension could be adjusted by adding a non-foaming surfactant.
- a sufficient buffer strength so that the pH
variation is less than 1 unit when 5 cc of decinormal (O.lN) HCl or 5 cc of (0.1N)NaOH is added to 100 cc of the fountain solution.
The concentrate of this invention is blended with water to comprise 1% to 6% of the fountain solution.
The resulting fountain solution has a pH between about 4.7 and about 5.3 and a surface tension between about 32 and 52 x 00~3 Newton/m. The fountain solution made with this invention will have a buffering effect such that the pH vartiation will be less than one pH unit if either a strong base or a strong acid is added to the solution. For example, if 5 cc of decinormal (O.lN)NaOH or decinormal (0.1N)HCl is added to 100 cc of the solution of this invention, the p~ variation will be less than one unitO With some preferred preparations of the invention, it is possible, with the same test to obtain pH variations which are less than 0.5 unit.
Czrboxylic acids which can be used to form the buffer salts of this invention are citric acid, malic, glutaric, succinic, azelaic acid and similar polyacids which have a PKa between about 3 and about 6. The polyacids used to form the buffer salts may have other functional groups, such as hydroxyl groups. The organic bases contemplated by this invention are the amines including primary, secondary and tertiary amines, polyamines such as hydrazine and ethylenediamine, cyclic amines and aminoalcohols.
These amines will have a PKb between about 2 and about 9 and preferab~y between 3 and 6.
A particularly useful buffer is the salt of citric acid and dimethylamine.
The PKa of a polycarboxylic acid - amine salt solution will vary in accordance with the number of acid groups which are neutralized on the polycarboxylic acid molecule by the organic base. It is preferred, according to my invention, to obtain buffer salts wherein a sufficient number of acid groups on the polycarboxylic acid molecule are unreacted in order to obtain the desired pH range of the fountain solution.
The fountain solution may contain, in addition to the above-described buffer, an hygroscopic product and an alcohol which homogeneize the different ingredients, additives such as a bactericide or an algicide, and detergents such as N-methyl pyrrolidone or various surfactants. The hygroscopic product may be glycerine or an equivalent polyol such as a polysaccharide or one of its derivatives (for example carboxymethylcellulose) or a vinylpyrrolidone polymer, or a colloidal silicic acid; it is used to maintain the quantity of water deposited on the plate and on the blanket. In fact, the water film thickness on the planographic plate is very thin due to the low surface tension of the fountain solutions of the invention. Consequently, the use of fountain solution is decreased during a typical press run. Another important technical consequence of the minimal amounts of water required by use of my invention is the faster drying of the prints. The .
62106-lS0 bactericide and/or algicide used in the concentrate of this inven-tion may be any such commercially available products. The term biocide as used herein refers to a bactericide, an algicide, or a combination thereor.
A particularly useful and preferred embodiment of my invention is a concentrate for use in lithographic fountain solu-tions, wherein the concentrate is mixed in an amount of about 6 wt.%
with water to form a fountain solution having a pH between 4.7 and 5.3, a surface tension between 32 and 52 x 10 3 Newton/m and sufficient buffer strength so that the pH variation is less than 1 unit when strong acids or bases are added to the solution, compris-ing:
- 58.7 wt.% water - 20.5 wt.% of a buffer salt solution comprising the salt of citric acid and dimethylamine - 7 wt.% of a hygroscopic product selected from the group eonsisting of glycerire and equivalent polyols, vinyl pyrrolidone, and colloidal silicic acid - 5.3 wt.% ethanol - 3.5 wt.% isopropanol - 5 wt.% bioeide As previously mentioned, the fountain solutions prepared from the eoncentrates of my invention when used with lithographic printing presses have demonstrated numerous beneEicial results which are both unexpected and surprising including accelerated drying time, decreased linting, improved rub resistance, decreased use of fountain solution and decreased use of alcohol. Although the reasons for the unexpected results are not clear, the inter-8~
actions of the fountain solution with the inks, the paper sub-strates, and the surface of the planographic plates are in my opinion - 8a -: ~,. 5 ' 1 the controlling factors. It is known in the art that the interaction of fountain solution with the ink and paper will affect the print characteristics and printing process characteristics. I have found that the novel fountain solutions of my invention when used in lithographic printing unexpextedly result in extremely thin layers of water being maintained on the hydrophilic portions of the plate. In addition, the strong buffering action of the buffer of my invention conpensates for the pH altering characteristics of various inks and paper substrates. Variations from an ideal pH range of 4.0 - 5.0 can have various adverse effects upon drying time, plate sensitivity, etc.
Although fountain solutions typically contain up to 15 wt.~ low molecular weight alcohols, the use of alcohol in the fountain solutions prepared with the concentrates of my invention are miniscule (~04 wt.% -1.2 wt.%3 and in the case of Dahlgren systems, can be eliminated, or substantially decreased.
The concentrations of buffer salts in the fountain solution concentrates of this invention range from about 7.0 wt.% to about 35.0 wt.~. The concentrations of buffer salts in the fountain solutions of this invention range from about .07 wt.% to about 2.1 wt.%.
It is contemplated that, in order to obtain the required buffering effect, individual buffer salts, combinations of buffer salts, or combinations of buffer salts and acids may be used to prepare the fountain solution concentrates of this invention.
~ 3~
The fountain solution concentrates of my invention will have the following ranges of components:
40.0 wt. % - 89.0 w-t.% water 7.0 wt.% - 35.0 wt.% buffer 5.0 wt.% - 20.0 wt.% a hygroscopic product, such as a polyol 0.0 wt.% - lO.0 wt.%(preEerably 4% - 10%)low molecular weight alcohol 0.0 wt.% - 0.1 wt.% surfactant 0.0 wt.% - 6.0 wt.% ~preferably 0.5% to 6%) Biocide Description of the Preferred Embodiments The following examples are given to further illustrate the invention but not to limit it in any way.
Example l A buffer salt was prepared by reacting one mole of citric acid (monohydra-ted) with 2 moles of dimethylamine. 0.6 gram of salt was mixed into lO0 grams of water to produce an aqueous sol-ution having the following properties:
pH = 5.3 Buffer effect:
The addition of 5 cc of decinormal (O.lN) sodium hydrox-ide varied the pH from 5.3 to 5.8.
The addition of 5 cc of decinormal (O.lN) hydrochloric acid varied the pH from 5.3 to 4.9.
Surface tension: = approximately 47.3 x lO 3 Newton/m.
In this example two acid groups of citric acid have been neutral-ized (the PKa f the second acid group being between 4.7 and 4.8).
a~
Example 2 A buffer salt was prepared by reacting 1 mole of monohydrated citric acid with 2 moles of ethanolamine.
0.6 gram of the buffer salt was mixed into 100 grams of water to produce an aqueous solution havng the following properties:
pH = 5.25 Buffer effect:
The addition of 5 cc of decinormal (0.1N) sodium hydroxide raised the pH to 5.8.
The addition of 5 cc of decinormal (0.1N) hydrochloric acid lowered the pH to 4.8 Surface tension = 42.6 x 10~3 Newton/m, approximately.
Example 3 A buffer salt was prepared by reacting 1 mole of malic acid with 1.1 moles of dimethylamine. 0.~ gram of this salt was mixed with 100 grams of water to form an aqueous solution having the following properties:
pH = 4.3 Buffer effect:
The addition of 5 cc of decinormal (0.1N) sodium hydroxide raised the pH to 4.7.
The addition of 5 cc of decinormal (0.1N) hydrochloric acid lowered the pH to 4.1.
Surface tension = 54O9 x 10 ~3 Newton/m approximately.
In this example we have neutralized slightly more than 1 acid group of malic acid (the PKa f the first acidic function being 3O4 and the PKa of the second acid group ~eing approximately 5.1).
Example 4 A buffer salt was prepared by reacting 1 mole of monohydrated citric acid with 2 moles of cyclohexylamine. 0.6 gram of this salt ~as mixed with S 100 grams of water to form an aqueous solution having the following characteristics:
pH = 5.4 Buffer effect:
The addition of 5 cc of decinormal (0.1N) sodium hydroxide raised the pH to 6.2.
The addition of 5 cc of decinormal (O.lN~ hydrogen chloride lowered the p~ to 4.9.
Surface tension~ = approximately 50.4 x 10-3 Newton/m.
Example 5 A buffer salt was prepared by reacting 1 mole of adipic acid with 1 mole of piperidine. 0.6 gram of this salt was mixed with 100 grams of water to form an aqueous solution having the following characteristics:
pH = 5 Buffer effect:
The addition of 5 cc of decinormal (O.lN) sodium hydroxide raised the pH to 5.3 The addition of 5 cc of decinormal (O.lN) hydrogen chloride lowered the pH to 4.7 Example 6 A buffer salt was prepared by reacting 1 mole of adipic acid with 1 mole of dimethylamine. 0.6 gram of this salt was mixed with 100 grams of water to form an aqueous solution having the following characteristics:
pH = 4.9 Buffer effect:
The addition of 5 cc of decinormal (O.lN) sodium hydroxide raised the pH to 5.1.
The addition of 5 cc of decinormal (0.1N) hydrogen chloride lowered the pH to 4.7.
Example 7 We obtained results equivalent to those obtained in Examples 1-6 using the following acids and bases:
Glutaric acid (1 mole) Cyclohexylamine (1 mole) Succinic acid (1 mole) Ethylenediamine (0.5 mole) Azelaic acid (1 mole) Triethylamine (1 mole) Example 8 Fountain Solution Concentrates Fountain Solution concentrates were prepared by combining the following ingredients, which are listed in parts by weight:
A s Buffer salts of Examples 1 to 7 30.0 32.2 Glycerine 18.0 13.6 Ethyl alcohol 5.4 4.5 Isopropyl alcohol3.6 2.8 Bactericide 0.9 0.9 Water 42.1 46.0 Total: 100.0 100.0 The concentrates as prepared in accordance with formulation A and B were mixed with water in a 30 proportion of 1 to 6 parts of concentrate to 100 parts of water to form fountain solutions.
Example 9 Other fountain solution concentrates were prepared by combining the following ingredients:
C D
Buffer salts of Examples 1 to 7 7.4 20.5 Polyvinylpyrrolidone 5.0 7.0 Ethyl alcohol 2.9 5.3 Isopropyl alcohol 1.9 3.5 Bactericide 3.0 5.0 Surfactant 0.080.05 Water 79.7258.65 Total 100.00100.00 The concentrates as prepared in accordance with formulation C and D were mixed with water in a proportion of 1 to 6 parts of concentrate to 100 parts of water to form fountain solutions.
The use of the fountain solutions of Examples 8 and 9 results in the following unexpected improvements with any kind of print.ing press over conventional fountain solutions:
a) decreased paper breakage b) decreased paper linting and difibration resulting in fewer stoppages to clean the blankets c) lower adherence of paper on the blanket d) decreased ink/water emulsification e) accelerated drying f) improved rub resistance of the print.
Although this invention has been shown and described with respect to deta.iled embodiments thereof, ~.~5~
it will be understood by those skilled in the art that various changes in form and detail thereof may be made without departing from the spirit and scope of the claimed invention.
Background Art The web offset and lithographic printing processes employ planographic plates which transfer ink to a blanket roll which, in turn, then transfers the ink to a substrate thereby forming the printed images. The plates are referred to as planographic since the image and non-image areas are in the same plane. The plates are constructed so that with proper treatment the image areas are hydrophobic and oleophilic and thereby receptive to inks. The non-image areas are hydrophilic and are water receptive. In order to maintain the hydrophilic characteristics of the non-image areas, and to prevent ink from accumulating on the non-image areas, it is necessary to continuously treat the plate with a water based fountain solution. The water based fountain solution can be applied to the plate with a separate roll prior to inking, or, the in]s and fountain solution can be applied simultaneously as in the Dahlgren type of system.
Although plain tap water can be used as a fountain solution, it is known in the art to include additional ingredients in combination with water as a fountain ~2~
solution in order to improve the printing characteristics. It is known to include low boiling point alcohols, such as isopropanol and ethanol, and various surfactants to reduce surface tension and permit better wetting of the plates. It is also known to include an acid or a buffer to achieve a pH range of 4.0 - 6Ø Polyols such as glycerine are introduced into a fountain solution to act as a humectant and lubricant, and to assist in maintaining a thin layer of water on the hydrophilic areas of the plate. Biocides such as bactericides and algicides are added to control microbiological growth in the fountain solution.
Typically, fountain solutions are prepared at the printing site by mixing fountain concentrates with tap water.
The use of fountain solutions has been found to have numerous beneficial effects upon the printing process including reduction of water ink emulsion, reduced scumming, reduced paper defibration, reduced paper breakage, accelerated drying, longer press runs, - etc.
A typical fountain solution known in the art contains ethyl alcohol or isopropyl alcohol, glycerine, surfactant, bactericide or algicide, various amounts of an acidifying agent such as phosphoric acid, and water.
U.S. Patent 4,247,328 to Lawson et al discloses lithographic fountain concentrates containing a desensitizing material. The preferred desensitizing materials disclosed are salts of acids such as citric acid, phosphoric acid, tartaric acid and EDTA. Lawson states that although acids can be used as a :L2~
desensiti~er, salts are preferred since they act as buffers to overcome the use of acidic or alkaline tap waters. Lawson requires the use of at least 50%
organic sol~ent in the fountain solution concentrate.
U.S. Patent 4,150,996 discloses a fountain solution concentrate containing sulfanilic acid, formaldehyde, sodium hydroxide, and gum arabic. Gum arabic has been found to have numerous negative effects including gumming and glazing of plates and rollers and promotion of the growth of bacteria and algae.
U.S. Patent 4,278,467 to Fadner discloses a fountain solution which contains a substitutive replacement for isopropyl alcohol.
U.S. Patent 4,116,896 to Garret et al discloses a fountain solution whereby detrimental precipitation is controlled in acidic alcohol/water fountain solutions by the use of a chelating agent.
Accordingly, what is needed in the art is an improved fountain solution with a strong buffering capacity which will maintain a given pH range over time duriog the printing process thereby resulting in improvements in said printing process. Additionally, the improved fountain solution should eliminate alcohol or contain drastically reduced quantities of alcohol.
Disclosure of Invention It has now been found that by formulating a fountain solution concentrate having a strong buffer formed by reacting a polycarboxylic acid with an organic base and mixing about 1.0 wt.% to 6.0 wt.~ of said concentrate with water, a fountain solution exhibiting a superior buffering effect and containing no alcohol or extremely small quanti-ties of alcohol is obtained. The result-ant fountain solution formed from a concentrate when used with a lithographic printing press results in the following unexpected and surprising improvements: longer press run, decreased scumming, decreased ink/water emulsification, decreased linting and difibra-tion, deereased substrate breakage, improved drying, decreased strike-in, and improved ink/water balance.
This invention relates to concentrates for use in litho-graphic fountain solutions. The concentrates are a bleildof abuffer, a hygroscopic product, such as a polyol, water, and prefer-ably an alcohol. The concentrates used on lithographic presses '- using a Dahlgren dampening system do not contain alcohol. The concentrates of this invention can additionally contain a bacter-icide or algicide, and surfactants. The concentrate is blended with tap water to form a fountain solution sueh that the eoncent-rate comprises 1% to 6% of the fountain solution. The buffers used in this invention are the salts of polycarboxylic acids and organic bases (amines). The polycarboxylic acids have a PKa between 3 and 6 while the bases must have a PKb between 2 and 9. The polycarboxy-lic acids may have at least one hydroxyl group.
Detailed Description of the Invention The presen-t invention is directed to a water base concent-rate for use in lithographic fountain solutions, wherein said con-centrate is mixed in an amount of about 1.0 wt.% to 6.0 wt.% with water to form a fountain 8~
solution, said fountain solution concentrate characterized by:
water;
a buffer salt, comprising the salt of polycarboxylic acid having a PKa between 3 and 6 and an organic base having a PKb between 2 and 9;
low molecular weight alcohols;
an hygroscopic product such as glycerine or an equivalent polyol such as a polysaccharide or one of its derivatives (for example carboxymethylcellulose) or a product resulting from the polymerisation of the vinylpyrrodone, or a colloidal silicic acid;
and various optional ingredients such as surfactants, bactericides and/or algicides;
wherein said fountain solution made by mixing the concentrate with water, has - a pH between about 4~7 and about 5.3, - a surface tension between about 32 x 10-3 Newton/m and about 52 x 10-3 Newton/m.
The surface tension is adjusted according to the type of dampening system. For classic dampening systems (water based systems) the surface tension will be selected preferably between about 44 and 52 x 10~3 Newton/m. For alcohol dampening systems, the surface tension will be preferably between about 32 and 37 x 10~3 Newton/m; in this case, by selecting the proper fountain additi~e, it will be possible to decrease or suppress the alcohol usually used in that dampening system. If it is necessary the surface tension could be adjusted by adding a non-foaming surfactant.
- a sufficient buffer strength so that the pH
variation is less than 1 unit when 5 cc of decinormal (O.lN) HCl or 5 cc of (0.1N)NaOH is added to 100 cc of the fountain solution.
The concentrate of this invention is blended with water to comprise 1% to 6% of the fountain solution.
The resulting fountain solution has a pH between about 4.7 and about 5.3 and a surface tension between about 32 and 52 x 00~3 Newton/m. The fountain solution made with this invention will have a buffering effect such that the pH vartiation will be less than one pH unit if either a strong base or a strong acid is added to the solution. For example, if 5 cc of decinormal (O.lN)NaOH or decinormal (0.1N)HCl is added to 100 cc of the solution of this invention, the p~ variation will be less than one unitO With some preferred preparations of the invention, it is possible, with the same test to obtain pH variations which are less than 0.5 unit.
Czrboxylic acids which can be used to form the buffer salts of this invention are citric acid, malic, glutaric, succinic, azelaic acid and similar polyacids which have a PKa between about 3 and about 6. The polyacids used to form the buffer salts may have other functional groups, such as hydroxyl groups. The organic bases contemplated by this invention are the amines including primary, secondary and tertiary amines, polyamines such as hydrazine and ethylenediamine, cyclic amines and aminoalcohols.
These amines will have a PKb between about 2 and about 9 and preferab~y between 3 and 6.
A particularly useful buffer is the salt of citric acid and dimethylamine.
The PKa of a polycarboxylic acid - amine salt solution will vary in accordance with the number of acid groups which are neutralized on the polycarboxylic acid molecule by the organic base. It is preferred, according to my invention, to obtain buffer salts wherein a sufficient number of acid groups on the polycarboxylic acid molecule are unreacted in order to obtain the desired pH range of the fountain solution.
The fountain solution may contain, in addition to the above-described buffer, an hygroscopic product and an alcohol which homogeneize the different ingredients, additives such as a bactericide or an algicide, and detergents such as N-methyl pyrrolidone or various surfactants. The hygroscopic product may be glycerine or an equivalent polyol such as a polysaccharide or one of its derivatives (for example carboxymethylcellulose) or a vinylpyrrolidone polymer, or a colloidal silicic acid; it is used to maintain the quantity of water deposited on the plate and on the blanket. In fact, the water film thickness on the planographic plate is very thin due to the low surface tension of the fountain solutions of the invention. Consequently, the use of fountain solution is decreased during a typical press run. Another important technical consequence of the minimal amounts of water required by use of my invention is the faster drying of the prints. The .
62106-lS0 bactericide and/or algicide used in the concentrate of this inven-tion may be any such commercially available products. The term biocide as used herein refers to a bactericide, an algicide, or a combination thereor.
A particularly useful and preferred embodiment of my invention is a concentrate for use in lithographic fountain solu-tions, wherein the concentrate is mixed in an amount of about 6 wt.%
with water to form a fountain solution having a pH between 4.7 and 5.3, a surface tension between 32 and 52 x 10 3 Newton/m and sufficient buffer strength so that the pH variation is less than 1 unit when strong acids or bases are added to the solution, compris-ing:
- 58.7 wt.% water - 20.5 wt.% of a buffer salt solution comprising the salt of citric acid and dimethylamine - 7 wt.% of a hygroscopic product selected from the group eonsisting of glycerire and equivalent polyols, vinyl pyrrolidone, and colloidal silicic acid - 5.3 wt.% ethanol - 3.5 wt.% isopropanol - 5 wt.% bioeide As previously mentioned, the fountain solutions prepared from the eoncentrates of my invention when used with lithographic printing presses have demonstrated numerous beneEicial results which are both unexpected and surprising including accelerated drying time, decreased linting, improved rub resistance, decreased use of fountain solution and decreased use of alcohol. Although the reasons for the unexpected results are not clear, the inter-8~
actions of the fountain solution with the inks, the paper sub-strates, and the surface of the planographic plates are in my opinion - 8a -: ~,. 5 ' 1 the controlling factors. It is known in the art that the interaction of fountain solution with the ink and paper will affect the print characteristics and printing process characteristics. I have found that the novel fountain solutions of my invention when used in lithographic printing unexpextedly result in extremely thin layers of water being maintained on the hydrophilic portions of the plate. In addition, the strong buffering action of the buffer of my invention conpensates for the pH altering characteristics of various inks and paper substrates. Variations from an ideal pH range of 4.0 - 5.0 can have various adverse effects upon drying time, plate sensitivity, etc.
Although fountain solutions typically contain up to 15 wt.~ low molecular weight alcohols, the use of alcohol in the fountain solutions prepared with the concentrates of my invention are miniscule (~04 wt.% -1.2 wt.%3 and in the case of Dahlgren systems, can be eliminated, or substantially decreased.
The concentrations of buffer salts in the fountain solution concentrates of this invention range from about 7.0 wt.% to about 35.0 wt.~. The concentrations of buffer salts in the fountain solutions of this invention range from about .07 wt.% to about 2.1 wt.%.
It is contemplated that, in order to obtain the required buffering effect, individual buffer salts, combinations of buffer salts, or combinations of buffer salts and acids may be used to prepare the fountain solution concentrates of this invention.
~ 3~
The fountain solution concentrates of my invention will have the following ranges of components:
40.0 wt. % - 89.0 w-t.% water 7.0 wt.% - 35.0 wt.% buffer 5.0 wt.% - 20.0 wt.% a hygroscopic product, such as a polyol 0.0 wt.% - lO.0 wt.%(preEerably 4% - 10%)low molecular weight alcohol 0.0 wt.% - 0.1 wt.% surfactant 0.0 wt.% - 6.0 wt.% ~preferably 0.5% to 6%) Biocide Description of the Preferred Embodiments The following examples are given to further illustrate the invention but not to limit it in any way.
Example l A buffer salt was prepared by reacting one mole of citric acid (monohydra-ted) with 2 moles of dimethylamine. 0.6 gram of salt was mixed into lO0 grams of water to produce an aqueous sol-ution having the following properties:
pH = 5.3 Buffer effect:
The addition of 5 cc of decinormal (O.lN) sodium hydrox-ide varied the pH from 5.3 to 5.8.
The addition of 5 cc of decinormal (O.lN) hydrochloric acid varied the pH from 5.3 to 4.9.
Surface tension: = approximately 47.3 x lO 3 Newton/m.
In this example two acid groups of citric acid have been neutral-ized (the PKa f the second acid group being between 4.7 and 4.8).
a~
Example 2 A buffer salt was prepared by reacting 1 mole of monohydrated citric acid with 2 moles of ethanolamine.
0.6 gram of the buffer salt was mixed into 100 grams of water to produce an aqueous solution havng the following properties:
pH = 5.25 Buffer effect:
The addition of 5 cc of decinormal (0.1N) sodium hydroxide raised the pH to 5.8.
The addition of 5 cc of decinormal (0.1N) hydrochloric acid lowered the pH to 4.8 Surface tension = 42.6 x 10~3 Newton/m, approximately.
Example 3 A buffer salt was prepared by reacting 1 mole of malic acid with 1.1 moles of dimethylamine. 0.~ gram of this salt was mixed with 100 grams of water to form an aqueous solution having the following properties:
pH = 4.3 Buffer effect:
The addition of 5 cc of decinormal (0.1N) sodium hydroxide raised the pH to 4.7.
The addition of 5 cc of decinormal (0.1N) hydrochloric acid lowered the pH to 4.1.
Surface tension = 54O9 x 10 ~3 Newton/m approximately.
In this example we have neutralized slightly more than 1 acid group of malic acid (the PKa f the first acidic function being 3O4 and the PKa of the second acid group ~eing approximately 5.1).
Example 4 A buffer salt was prepared by reacting 1 mole of monohydrated citric acid with 2 moles of cyclohexylamine. 0.6 gram of this salt ~as mixed with S 100 grams of water to form an aqueous solution having the following characteristics:
pH = 5.4 Buffer effect:
The addition of 5 cc of decinormal (0.1N) sodium hydroxide raised the pH to 6.2.
The addition of 5 cc of decinormal (O.lN~ hydrogen chloride lowered the p~ to 4.9.
Surface tension~ = approximately 50.4 x 10-3 Newton/m.
Example 5 A buffer salt was prepared by reacting 1 mole of adipic acid with 1 mole of piperidine. 0.6 gram of this salt was mixed with 100 grams of water to form an aqueous solution having the following characteristics:
pH = 5 Buffer effect:
The addition of 5 cc of decinormal (O.lN) sodium hydroxide raised the pH to 5.3 The addition of 5 cc of decinormal (O.lN) hydrogen chloride lowered the pH to 4.7 Example 6 A buffer salt was prepared by reacting 1 mole of adipic acid with 1 mole of dimethylamine. 0.6 gram of this salt was mixed with 100 grams of water to form an aqueous solution having the following characteristics:
pH = 4.9 Buffer effect:
The addition of 5 cc of decinormal (O.lN) sodium hydroxide raised the pH to 5.1.
The addition of 5 cc of decinormal (0.1N) hydrogen chloride lowered the pH to 4.7.
Example 7 We obtained results equivalent to those obtained in Examples 1-6 using the following acids and bases:
Glutaric acid (1 mole) Cyclohexylamine (1 mole) Succinic acid (1 mole) Ethylenediamine (0.5 mole) Azelaic acid (1 mole) Triethylamine (1 mole) Example 8 Fountain Solution Concentrates Fountain Solution concentrates were prepared by combining the following ingredients, which are listed in parts by weight:
A s Buffer salts of Examples 1 to 7 30.0 32.2 Glycerine 18.0 13.6 Ethyl alcohol 5.4 4.5 Isopropyl alcohol3.6 2.8 Bactericide 0.9 0.9 Water 42.1 46.0 Total: 100.0 100.0 The concentrates as prepared in accordance with formulation A and B were mixed with water in a 30 proportion of 1 to 6 parts of concentrate to 100 parts of water to form fountain solutions.
Example 9 Other fountain solution concentrates were prepared by combining the following ingredients:
C D
Buffer salts of Examples 1 to 7 7.4 20.5 Polyvinylpyrrolidone 5.0 7.0 Ethyl alcohol 2.9 5.3 Isopropyl alcohol 1.9 3.5 Bactericide 3.0 5.0 Surfactant 0.080.05 Water 79.7258.65 Total 100.00100.00 The concentrates as prepared in accordance with formulation C and D were mixed with water in a proportion of 1 to 6 parts of concentrate to 100 parts of water to form fountain solutions.
The use of the fountain solutions of Examples 8 and 9 results in the following unexpected improvements with any kind of print.ing press over conventional fountain solutions:
a) decreased paper breakage b) decreased paper linting and difibration resulting in fewer stoppages to clean the blankets c) lower adherence of paper on the blanket d) decreased ink/water emulsification e) accelerated drying f) improved rub resistance of the print.
Although this invention has been shown and described with respect to deta.iled embodiments thereof, ~.~5~
it will be understood by those skilled in the art that various changes in form and detail thereof may be made without departing from the spirit and scope of the claimed invention.
Claims (26)
1. An improved water dilutable concentrate for use in lithographic fountain solutions containing water, a buffer, a polyol and a surfactant, characterized by:
an improved buffer comprising at least one salt of (a) a polycarboxylic acid and (b) an organic amine, wherein the polycarboxylic acid has a PKa between about 3 and about 6, the organic amine has a PKb between about 2 and about 9, and the concentrate when mixed in an amount of about 1% to about 6% by weight with water yields a fountain solution having a pH between about 4.7 and about 5.3, a surface tension between about 32 x 10-3 Newton/m and about 52 x 10-3 Newton/m, and a sufficient buffer effect such that the pH
variation of the fountain solution will be less than about one pH unit when 5 cc of decinormal NaOH or 5 cc of decinormal HCl is added to 100 cc of the fountain solution.
an improved buffer comprising at least one salt of (a) a polycarboxylic acid and (b) an organic amine, wherein the polycarboxylic acid has a PKa between about 3 and about 6, the organic amine has a PKb between about 2 and about 9, and the concentrate when mixed in an amount of about 1% to about 6% by weight with water yields a fountain solution having a pH between about 4.7 and about 5.3, a surface tension between about 32 x 10-3 Newton/m and about 52 x 10-3 Newton/m, and a sufficient buffer effect such that the pH
variation of the fountain solution will be less than about one pH unit when 5 cc of decinormal NaOH or 5 cc of decinormal HCl is added to 100 cc of the fountain solution.
2. The concentrate of claim 1 which additionally contains 4 wt.% - 10 wt.% of a low molecular weight alcohol.
3. The concentrate as recited in claim 1 wherein the polycarboxylic acid is citric acid and the organic amine is dimethyl amine.
4. The concentrate as recited in claim 2 additionally containing 0.5 wt.% - 6.0 wt.% of a biocide.
5. The concentrate as recited in claim 3 additionally con-taining 0.5 wt.% - 6.0 wt.% of a biocide selected from the group consisting of algicide, bactericide, and a combination thereof.
6. The concentrate as recited in claim 1 wherein the poly-carboxylic acid contains at least one hydroxyl group.
7. The concentrate as recited in claim 2 wherein the low molecular weight alcohol is selected from the group consisting of ethanol, isopropanol, and a mixture thereof.
8. A water dilutable concentrate for use in lithographic fountain solutions which comprises:
58.7 wt.% water 20.5 wt.% of a buffer salt comprising the salt of citric acid and dimethylamine.
7 wt.% of a hygroscopic product selected from the group con-sisting of glycerine and equivalent polyols, polymer of vinvl Pyrrolidone and colloidal silicic acid 5.3 wt.% of ethanol 3.5 wt.% isopropanol 5.0 wt.% biocide wherein said concentrate, when mixed with water in an amount of about 1% to about 6% by weight, yields a fountain solution having a pH between about 4.7 and about 5.3, a surface tension between about 32 x 10-3 Newton/m and about 52 x 10-3 Newton/m, and a sufficient buffer effect such that the pH variation will be less than about one pH unit when 5 cc of decinormal NaOH or decinormal HCl is added to 100 cc of the fountain solution.
58.7 wt.% water 20.5 wt.% of a buffer salt comprising the salt of citric acid and dimethylamine.
7 wt.% of a hygroscopic product selected from the group con-sisting of glycerine and equivalent polyols, polymer of vinvl Pyrrolidone and colloidal silicic acid 5.3 wt.% of ethanol 3.5 wt.% isopropanol 5.0 wt.% biocide wherein said concentrate, when mixed with water in an amount of about 1% to about 6% by weight, yields a fountain solution having a pH between about 4.7 and about 5.3, a surface tension between about 32 x 10-3 Newton/m and about 52 x 10-3 Newton/m, and a sufficient buffer effect such that the pH variation will be less than about one pH unit when 5 cc of decinormal NaOH or decinormal HCl is added to 100 cc of the fountain solution.
9. An improved lithographic fountain solution containing water, a buffer, a polyol and a surfactant which comprises:
an improved buffer comprising at least one salt of (a) a polycarboxylic acid and (b) an organic amine, wherein the poly-carboxylic acid has a PKb between about 3 and about 6, the organic amine has a PKb between about 2 and about 9, and the fountain solution has a pH of between about 4.7 and about 5.3, a surface tension between about 32 x 10-3 Newton/m and about 52 x 10-3 Newton /m, and a sufficient buffer effect such that the pH variation will be less than about one pH unit when 5 cc of the decinormal NaOH or decinormal HCl is added to 100 cc of the fountain solution.
an improved buffer comprising at least one salt of (a) a polycarboxylic acid and (b) an organic amine, wherein the poly-carboxylic acid has a PKb between about 3 and about 6, the organic amine has a PKb between about 2 and about 9, and the fountain solution has a pH of between about 4.7 and about 5.3, a surface tension between about 32 x 10-3 Newton/m and about 52 x 10-3 Newton /m, and a sufficient buffer effect such that the pH variation will be less than about one pH unit when 5 cc of the decinormal NaOH or decinormal HCl is added to 100 cc of the fountain solution.
10. The fountain solution of claim 9 additionally containing 0.04 wt.% - 0.6 wt.% of a low molecular weight alcohol.
11. The fountain solution of claim 9 wherein the polycarboxy-lic acid is citric acid and the organic base is dimethyl amine.
12. The fountain solution of claim 9 additionally containing 0.005 wt.% - 0.36 wt.% of a biocide.
13. The fountain solution of claim 9 additionally containing 0.005 wt.% - 0.36 wt.% of a biocide selected from the group con-sisting of algicide, bactericide or a combination thereof.
14. The fountain solution of claim 9 wherein the polycarboxy-lic acid contains at least one hydroxyl group.
15. The fountain solution of claim 10 wherein the low mole-cular weight alcohol is selected from the group consisting of ethanol, isopropanol and a combination thereof.
16. In a method of lithographic or web-offset printing com-prising the preparation of a fountain solution by mixing a water dilutable fountain solution concentrate in an amount of about 1.0 wt.% to 6.0 wt.% with water wherein said fountain solution concen-trate contains water, a buffer, a polyol and surfactant, and then treating a planographic plate with said fountain solution such that the non-image areas of said plate are rendered hydrophilic, thereby inhibiting the deposition of ink on said areas and improv-ing the printing process, the improvement which comprises:
an improved buffer in the fountain solution comprising at least one salt of (a) a polycarboxylic acid and (b) an organic amine, wherein the polycarboxylic acid has a PKa between about 3 and about 6, the organic amine has a PKb between about 2 and about 9, said fountain solution having a pH between about 4.7 and about 5.3, a surface tension between about 32 x 10-3 Newton/m and about 52 x 10-3 Newton/m and sufficient buffer effect such that the pH
variation will be less than about one pH unit when 5 cc of the decinormal HC1 is added to 100 cc of said fountain solution.
an improved buffer in the fountain solution comprising at least one salt of (a) a polycarboxylic acid and (b) an organic amine, wherein the polycarboxylic acid has a PKa between about 3 and about 6, the organic amine has a PKb between about 2 and about 9, said fountain solution having a pH between about 4.7 and about 5.3, a surface tension between about 32 x 10-3 Newton/m and about 52 x 10-3 Newton/m and sufficient buffer effect such that the pH
variation will be less than about one pH unit when 5 cc of the decinormal HC1 is added to 100 cc of said fountain solution.
17. The method of claim 16 wherein the fountain solution additionally contains 0.04 wt.% - 0.6 wt.% of low molecular weight alcohol.
18. The method of claim 16 wherein the buffer salt in the fountain solution is the salt of citric acid and dimethyl amine.
19. The method of claim 16 wherein the fountain solution additionally contains 0.005 wt.% - 0.36 wt.% of a biocide.
20. The method of claim 16 wherein the fountain solution additionally contains 0.005 wt.% - 0.36 wt.% of a biocide selected from the group consisting of algicide, bactericide, and a combina-tion thereof.
21. The method of claim 16 wherein the polycarboxylic acid used to form the buffer salt of the fountain solution contains at least one hydroxyl group.
22. The method of claim 17 wherein the low molecular weight alcohol is selected from the group consisting of ethanol, isopropan-ol, and a combination thereof.
23. An improved water dilutable concentrate for a lithographic fountain solution containing water, a buffer, a hygroscopic product selected from the group consisting of glycerine or an equivalent polyol, polymer of vinyl pyrrolidone and colloidal silicic acid and a surfactant characterized by: an improved buffer comprising at least one salt of (a) a polycarboxylic acid and (b) an organic amine, wherein the polycarboxylic acid has a pKa between about 3 and about 6, the organic amine has a PKb between about 2 and about 9, and the concentrate when mixed in an amount of about 1% to about 6% by weight with water yields a fountain solution having a pH between about 4.7 and about 5.3, a surface tension between about 32 x 10-3 Newton/m and about 52 x 10-3 Newton/m, and a suffi-cient buffer effect such that the pH variation of the fountain solution will be less than about one pH unit when 5 cc of decin-ormal NaOH or 5 cc of decinormal HCl is added to 100 cc of the fountain solution.
24. An improved lithographic fountain solution comprising water, a buffer, a hygroscopic product selected from the group consisting of glycerine or an equivalent polyol, a polymer of vinyl pyrrolidone and colloidal silicic acid and a surfactant which solution comprises:
an improved buffer comprising at least one salt of (a) a poly-carboxylic acid and (b) an organic amine, wherein the polycarboxylic acid has a PKb between about 3 and about 6, the organic amine has a PKb between about 2 and about 9, and the fountain solution has a pH
of between about 4.7 and about 5.3, a surface tension between about 32 x 10-3 Newton/m and about 52 x 10-3 Newton/m, and a sufficient buffer effect such that the pH variation will be less than about one pH unit when 5 cc of the decinormal NaOH or 5 cc of decinormal HCl is added to 100 cc of the fountain solution.
an improved buffer comprising at least one salt of (a) a poly-carboxylic acid and (b) an organic amine, wherein the polycarboxylic acid has a PKb between about 3 and about 6, the organic amine has a PKb between about 2 and about 9, and the fountain solution has a pH
of between about 4.7 and about 5.3, a surface tension between about 32 x 10-3 Newton/m and about 52 x 10-3 Newton/m, and a sufficient buffer effect such that the pH variation will be less than about one pH unit when 5 cc of the decinormal NaOH or 5 cc of decinormal HCl is added to 100 cc of the fountain solution.
25. A water dilutable concentrate of a buffer for use in a lithographic fountain solution comprising water, a buffer, a polyol and a surfactant, which concentrate comprises a buffer comprising at least one salt of (a) polycarboxylic acid and (b) an organic amine, wherein the polycarboxylic acid has a PKa between about 3 and about 6, the organic amine has a PKb between about 2 and about 9 and the concentrate when mixed to form an amount of about 1% to 6% by weight of a fountain solution yields a fountain solution having a pH between about 4.7 and 5.3, a surface tension between about 32 x 10-3 Newton/m and about 52 x 10-3 Newton/m, and a sufficient buffer effect such that the pH variation of the fountain solution will be less than about one pH unit when 5 cc of decinorm-al NaOH or 5 cc of decinormal HCl is added to 100 cc of the foun-tain solution.
26. A water dilutable concentrate for use in a lithographic fountain solution which concentrate comprises water, a buffer, and a hygroscopic product selected from glycerine or an equivalent hygroscopic polyol, polymer of vinyl pyrrolidone and colloidal silica wherein said buffer comprises at least one salt of (a) a polycarboxylic acid and (b) an organic amine, wherein the polycarboxylic acid has a PKa between about 3 and 6, the organic amine has a PKb between about 2 and about 9, and the concentrate when mixed in an amount of about 1% to about 6% by weight with water yields a fountain solution having a pH between about 4.7 and about 5.3, a surface tension between about 32x10 3 Newton/m and about 52 x 10 3 Newton/m, and a sufficient buffer effect such that the pH variation of the fountain solution will be less than about one pH unit when 5 cc of decinormal NaOH or 5 cc of decinormal HCl is added to 100 cc of the fountain solution.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8219911A FR2536675A1 (en) | 1982-11-26 | 1982-11-26 | COMPOSITIONS FOR WATER OFFSET PLATE WET |
| FR8219911 | 1982-11-26 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1251881A true CA1251881A (en) | 1989-03-28 |
Family
ID=9279581
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000441981A Expired CA1251881A (en) | 1982-11-26 | 1983-11-25 | Lithographic water based fountain solution concentrates |
Country Status (8)
| Country | Link |
|---|---|
| EP (2) | EP0126773A1 (en) |
| JP (1) | JPS59502097A (en) |
| AU (1) | AU576748B2 (en) |
| CA (1) | CA1251881A (en) |
| DK (1) | DK541683A (en) |
| FR (1) | FR2536675A1 (en) |
| MX (1) | MX161896A (en) |
| WO (1) | WO1984002142A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4859247A (en) * | 1987-11-02 | 1989-08-22 | Basf Corporation | Low viscosity, highly concentrated pigment dispersions and method of making same |
| US4822419A (en) * | 1987-11-09 | 1989-04-18 | Basf Corporation | Lithographic ink composition and process for making same |
| IT1266557B1 (en) * | 1993-07-21 | 1997-01-09 | Arturo Guerini | PROCEDURE AND EQUIPMENT FOR TREATMENT OF WET LIQUID IN PRINTING MACHINES, ESPECIALLY FOR |
| EP0667243A1 (en) * | 1994-02-15 | 1995-08-16 | Saito, Toshiki, c/o Toshiki Saito Design Room | Offset printing method and high-density mini-prints produced by the method |
| WO1999050076A1 (en) * | 1998-03-31 | 1999-10-07 | B/M Management Cc | Printing solution for lithographic printing |
| JP5805149B2 (en) * | 2012-07-17 | 2015-11-04 | 東京インキ株式会社 | Lithographic printing method and fountain solution concentrated composition |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3083149A (en) * | 1959-10-12 | 1963-03-26 | Universal Oil Prod Co | Method of masking a surface with a salt of a carboxylic acid and an aminoalkane prior to dyeing |
| US3398002A (en) * | 1967-06-29 | 1968-08-20 | Bondurant | Universal fountain solution for planographic printing |
| GB1441588A (en) * | 1972-10-04 | 1976-07-07 | Unilever Ltd | Rinse composition |
| PL91463B1 (en) * | 1974-08-23 | 1977-02-28 | ||
| GB1602823A (en) * | 1978-01-18 | 1981-11-18 | Vickers Ltd | Lithographic printing |
| JPS55115045A (en) * | 1979-02-27 | 1980-09-04 | Fuji Photo Film Co Ltd | Printing plate preparation |
| JPH0237316B2 (en) * | 1981-02-25 | 1990-08-23 | Seisan Kaihatsu Kagaku Kenkyusho | INSATSUHANYOKIBANOYOBI INSATSUHAN |
-
1982
- 1982-11-26 FR FR8219911A patent/FR2536675A1/en not_active Withdrawn
-
1983
- 1983-11-18 EP EP84900335A patent/EP0126773A1/en not_active Withdrawn
- 1983-11-18 JP JP84500418A patent/JPS59502097A/en active Pending
- 1983-11-18 AU AU24122/84A patent/AU576748B2/en not_active Ceased
- 1983-11-18 WO PCT/US1983/001839 patent/WO1984002142A1/en unknown
- 1983-11-24 EP EP83402270A patent/EP0112745A1/en not_active Withdrawn
- 1983-11-25 MX MX199538A patent/MX161896A/en unknown
- 1983-11-25 DK DK541683A patent/DK541683A/en not_active Application Discontinuation
- 1983-11-25 CA CA000441981A patent/CA1251881A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DK541683D0 (en) | 1983-11-25 |
| AU2412284A (en) | 1984-06-18 |
| DK541683A (en) | 1984-05-27 |
| WO1984002142A1 (en) | 1984-06-07 |
| MX161896A (en) | 1991-02-28 |
| EP0126773A1 (en) | 1984-12-05 |
| AU576748B2 (en) | 1988-09-08 |
| FR2536675A1 (en) | 1984-06-01 |
| EP0112745A1 (en) | 1984-07-04 |
| JPS59502097A (en) | 1984-12-20 |
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