CA2865433C - Natural oil derived gelled ink vehicles - Google Patents
Natural oil derived gelled ink vehicles Download PDFInfo
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- CA2865433C CA2865433C CA2865433A CA2865433A CA2865433C CA 2865433 C CA2865433 C CA 2865433C CA 2865433 A CA2865433 A CA 2865433A CA 2865433 A CA2865433 A CA 2865433A CA 2865433 C CA2865433 C CA 2865433C
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- 239000000203 mixture Substances 0.000 claims abstract description 21
- 238000009472 formulation Methods 0.000 claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 3
- 239000006185 dispersion Substances 0.000 claims description 12
- 238000006386 neutralization reaction Methods 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 238000006596 Alder-ene reaction Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 150000003626 triacylglycerols Chemical class 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 241000219495 Betulaceae Species 0.000 claims 1
- 235000005911 diet Nutrition 0.000 claims 1
- 230000037213 diet Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- 230000002427 irreversible effect Effects 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 56
- 235000019198 oils Nutrition 0.000 description 56
- 239000000499 gel Substances 0.000 description 38
- 239000003549 soybean oil Substances 0.000 description 26
- 235000012424 soybean oil Nutrition 0.000 description 26
- 239000003981 vehicle Substances 0.000 description 23
- 239000000976 ink Substances 0.000 description 19
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 14
- 239000000944 linseed oil Substances 0.000 description 11
- 235000021388 linseed oil Nutrition 0.000 description 11
- 239000011541 reaction mixture Substances 0.000 description 10
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 9
- 229920000180 alkyd Polymers 0.000 description 7
- 235000010469 Glycine max Nutrition 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 239000004927 clay Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 238000005698 Diels-Alder reaction Methods 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000000159 acid neutralizing agent Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 235000019485 Safflower oil Nutrition 0.000 description 1
- 235000019486 Sunflower oil Nutrition 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012374 esterification agent Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 235000005713 safflower oil Nutrition 0.000 description 1
- 239000003813 safflower oil Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002600 sunflower oil Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 239000002383 tung oil Substances 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
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
- C09D11/06—Printing inks based on fatty oils
-
- 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
- C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F7/00—Chemical modification of drying oils
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Novel natural oil derived ink vehicles are provided by a two step process that does not require the addition of gelants or the irreversible heat bodying or polymerization of the oil. The gelled natural oil may be used as the vehicle/carrier in the ink formulation or alternatively used as a carrier or dispersant for additves in ink formulations. The gelled ink vehicles disclosed have many advantages over ink vehicles disclosed in the prior art.
Description
NATURAL OIL DERIVED GELLED INK VEHICLES
BACKGROUND OF THE INVENTION
The primary component of lithographic printing inks is a gelatinous or gelled vehicle or carrier that must possess sufficient viscosity to disperse finely divided pigments, anti-abrasion additives, and other solid components. Historically, the vehicle or carrier has been based on hydrocarbon based resins, and the control of the rheology of the ink vehicle has historically been challenging. In order to achieve the required gel structure, gelants must be added to the resin.
Typical gelants are the aluminum acylates or alkoxides as described in US
5,427,615 and modified clays as described in US 4,193,806. Other molecular gelants such as polyamide resins and styrene-butadiene block copolymers have been used as gelants in hydrocarbon based oils and solvents. There are several undesirable aspects associated with the use of these gelants.
Organoaluminum based gelants are typically provided in solvents at low concentration of the active aluminum component thus increasing the percentage of VOC's in the formulation. Heat is required for gelation to occur and precise temperature control is required or the gel structure can be destroyed. The modified clays also require heat and sometimes high shear is required to activate or open the clay structure in order for gelation to occur. Polyamide and block copolymer based gelants must be used at high weight percent loadings, typically 20 percent or higher, in order to achieved the desired viscosity. In addition all of these gelants add substantially to the cost of the ink vehicle.
There has been considerable interest in developing vehicles or earners for oil-based printing inks that do not require petroleum or hydrocarbon based components. Decreasing supplies of petroleum, environmental concerns, and interest in biodegradable and renewable resources have prompted the ink manufacturers to initiate efforts to develop inks with vehicles based on biodegradable materials to reduce the industry's dependency on petroleum. 1) ("Vegetable-Oil-Based Printing Ink Formulation and Degradation". Erhan, S.Z, Bagby, M.O.
Industrial Crops and Products. 3 (1995). 237-246. 2) "Vegetable Oil-Based Printing Inks".
Erhan, S.Z, Bagby, M.O. JAOCS, Vol. 69, no. 3 (1992) 251.
The primary means for increasing the viscosity or gelation of natural oils has historically been referred to as "heat-bodying" the oil. In this process, unsaturated natural oils are subjected to high temperatures, typically 300-340 deg C in an inert atmosphere in order to promote chemical crosslinking at the sites of unsaturation in the triglyceride oil.
This process as described in US 5,122,188 and US 6,418,852 typically results in oils with viscosities in the range 1600-1800 centipoise. In order to obtain higher viscosities, a second type of heat-bodying process Is employed in which the high temperature heating is continued until the oil is irreversibly gelled. This intractable gel is then heated at about 340 deg C
with unmodified oil to produce the desired viscosity. It is often necessary to filter insoluble clumps of gelled oil from these blends. In addition, because both of these processes result in irreversible chemical crosslinks between the triglyceride oil chains; it is difficult to maintain obtain precise control of the viscosity. Both of these processes also require rigorous exclusion of oxygen in order to prevent oil degradation and discoloration.
The present invention discloses gelled natural oils useful as ink vehicles and a novel method for their production. The natural oil gelled ink vehicles of the present invention offer several advantages over gelled vehicles disclosed in prior art in that no gelants are required and "heat-bodying" of the oil is unnecessary. The viscosities of the natural oil gelled ink vehicles may also be precisely controlled.
OBJECTS OF THE PRESENT INVENTION
It is an object of the present invention to provide biodegradable natural oil derived gelled vehicle/carrier compositions that can be incorporated into ink and coating formulations.
BACKGROUND OF THE INVENTION
The primary component of lithographic printing inks is a gelatinous or gelled vehicle or carrier that must possess sufficient viscosity to disperse finely divided pigments, anti-abrasion additives, and other solid components. Historically, the vehicle or carrier has been based on hydrocarbon based resins, and the control of the rheology of the ink vehicle has historically been challenging. In order to achieve the required gel structure, gelants must be added to the resin.
Typical gelants are the aluminum acylates or alkoxides as described in US
5,427,615 and modified clays as described in US 4,193,806. Other molecular gelants such as polyamide resins and styrene-butadiene block copolymers have been used as gelants in hydrocarbon based oils and solvents. There are several undesirable aspects associated with the use of these gelants.
Organoaluminum based gelants are typically provided in solvents at low concentration of the active aluminum component thus increasing the percentage of VOC's in the formulation. Heat is required for gelation to occur and precise temperature control is required or the gel structure can be destroyed. The modified clays also require heat and sometimes high shear is required to activate or open the clay structure in order for gelation to occur. Polyamide and block copolymer based gelants must be used at high weight percent loadings, typically 20 percent or higher, in order to achieved the desired viscosity. In addition all of these gelants add substantially to the cost of the ink vehicle.
There has been considerable interest in developing vehicles or earners for oil-based printing inks that do not require petroleum or hydrocarbon based components. Decreasing supplies of petroleum, environmental concerns, and interest in biodegradable and renewable resources have prompted the ink manufacturers to initiate efforts to develop inks with vehicles based on biodegradable materials to reduce the industry's dependency on petroleum. 1) ("Vegetable-Oil-Based Printing Ink Formulation and Degradation". Erhan, S.Z, Bagby, M.O.
Industrial Crops and Products. 3 (1995). 237-246. 2) "Vegetable Oil-Based Printing Inks".
Erhan, S.Z, Bagby, M.O. JAOCS, Vol. 69, no. 3 (1992) 251.
The primary means for increasing the viscosity or gelation of natural oils has historically been referred to as "heat-bodying" the oil. In this process, unsaturated natural oils are subjected to high temperatures, typically 300-340 deg C in an inert atmosphere in order to promote chemical crosslinking at the sites of unsaturation in the triglyceride oil.
This process as described in US 5,122,188 and US 6,418,852 typically results in oils with viscosities in the range 1600-1800 centipoise. In order to obtain higher viscosities, a second type of heat-bodying process Is employed in which the high temperature heating is continued until the oil is irreversibly gelled. This intractable gel is then heated at about 340 deg C
with unmodified oil to produce the desired viscosity. It is often necessary to filter insoluble clumps of gelled oil from these blends. In addition, because both of these processes result in irreversible chemical crosslinks between the triglyceride oil chains; it is difficult to maintain obtain precise control of the viscosity. Both of these processes also require rigorous exclusion of oxygen in order to prevent oil degradation and discoloration.
The present invention discloses gelled natural oils useful as ink vehicles and a novel method for their production. The natural oil gelled ink vehicles of the present invention offer several advantages over gelled vehicles disclosed in prior art in that no gelants are required and "heat-bodying" of the oil is unnecessary. The viscosities of the natural oil gelled ink vehicles may also be precisely controlled.
OBJECTS OF THE PRESENT INVENTION
It is an object of the present invention to provide biodegradable natural oil derived gelled vehicle/carrier compositions that can be incorporated into ink and coating formulations.
2 Another object of the present invention is to provide biodegradable natural oil derived gelled vehicle/carrier compositions that are derived from a renewable resource in place of non-renewable petroleum based compositions.
A further object of the present invention is to provide biodegradable natural oil derived gelled vehicle/carrier compositions that do not require the addition of gelants in order to achieve desired viscosities.
An additional object of the present invention is to provide biodegradable natural oil derived gelled vehicle/carrier compositions that do not require high temperature "heat-bodying" of the oil.
A still further object of the present invention is to provide biodegradable natural oil derived gelled compositions useful as vehicles for additives in ink formulations.
MILE juacHmuja Figure 1 shows that the viscosity may be controlled by the amount of neutralization of the maleic anhydride moieties.
Figure 2 shows the precise viscosity control of the vehicle that can be achieved by varying the percentage of the theoretical stoichiometric amount of triethanolamine added.
Figure 3 illustrates clay loadings of up to 75 percent achieved with a soybean oil gel of Example 11 while loadings of only 50 percent were achieved with the standard soy based alkyd resin.
SUMMARY OF THE INVENTION
The instant invention provides a gelled printing vehicle for heatset or other lithographic printing comprising an adduct derived from the reaction product of a natural unsaturated triglyceride oil, or derivative with a substrate suitable for Diels Alder reaction or Ene reaction and wherein said adduct is reacted in a non-aqueous neutralization reaction with a suitable base to form an ionomeric anhydrous gel.
A further object of the present invention is to provide biodegradable natural oil derived gelled vehicle/carrier compositions that do not require the addition of gelants in order to achieve desired viscosities.
An additional object of the present invention is to provide biodegradable natural oil derived gelled vehicle/carrier compositions that do not require high temperature "heat-bodying" of the oil.
A still further object of the present invention is to provide biodegradable natural oil derived gelled compositions useful as vehicles for additives in ink formulations.
MILE juacHmuja Figure 1 shows that the viscosity may be controlled by the amount of neutralization of the maleic anhydride moieties.
Figure 2 shows the precise viscosity control of the vehicle that can be achieved by varying the percentage of the theoretical stoichiometric amount of triethanolamine added.
Figure 3 illustrates clay loadings of up to 75 percent achieved with a soybean oil gel of Example 11 while loadings of only 50 percent were achieved with the standard soy based alkyd resin.
SUMMARY OF THE INVENTION
The instant invention provides a gelled printing vehicle for heatset or other lithographic printing comprising an adduct derived from the reaction product of a natural unsaturated triglyceride oil, or derivative with a substrate suitable for Diels Alder reaction or Ene reaction and wherein said adduct is reacted in a non-aqueous neutralization reaction with a suitable base to form an ionomeric anhydrous gel.
3 The invention also relates to a gelled printing vehicle for heatset or other lithographic printing comprising an adduct derived from the reaction product of an unsaturated triglyceride oil, or derivative with a substrate suitable for Diels Alder reaction or Ene reaction; said adduct being reacted in a non-aqueous neutralization/esterification reaction with an alkanolamine to form an ionomeric anhydrous gel.
DETAILED DESCRIPTION OF THE PRESENT INVENTION
The present invention provides gelled vehicles for non-aqueous ink formulations that are derived from natural oils. Thermoreversible gels of unsaturated natural oils of any desired viscosity are conveniently obtained by a simple economical two step process. This process has been described in detail in Applicant's U.S. co-pending application 13/776,542 filed February 25, 2013 and will be summarized here.
In the first step, the unsaturated natural oil, fatty acid or derivative thereof is modified by a process in which the double bonds and/or conjugated double bonds of the triglyceride oil chains are reacted via thermal condensation with an unsaturated substrate which is capable of undergoing an "ene" reaction or an Diels Alder reaction with the sites of unsaturation resulting in the formation of an adduct of the triglyceride oil. The adduct formed is preferentially an anhydride and the substrate reacted in this manner with the triglyceride oil is preferably maleic anhydride. The term "maleation"
been historically applied to the reaction of natural unsaturated oils, fatty acids and their derivatives.
Functionaliztion of triglyceride oils by this method is well known in the art and is described in US
2,033,131, 2,033,132 and 2,063,540. These adducts are generally referred to in the literature as "maleated oils" or maleinized oils". The aqueous neutralization of these natural oil adducts is also well known in the art to produce soaps, emulsifiers and water-based lubricants.
The method described in co-pending application 13/776,542 involves the controlled non-aqueous neutralization of such adducts to provide thermoreversible ionomeric gels. As described in co-pending application 13/776,542 either an alkali or alkaline earth metal base may be employed
DETAILED DESCRIPTION OF THE PRESENT INVENTION
The present invention provides gelled vehicles for non-aqueous ink formulations that are derived from natural oils. Thermoreversible gels of unsaturated natural oils of any desired viscosity are conveniently obtained by a simple economical two step process. This process has been described in detail in Applicant's U.S. co-pending application 13/776,542 filed February 25, 2013 and will be summarized here.
In the first step, the unsaturated natural oil, fatty acid or derivative thereof is modified by a process in which the double bonds and/or conjugated double bonds of the triglyceride oil chains are reacted via thermal condensation with an unsaturated substrate which is capable of undergoing an "ene" reaction or an Diels Alder reaction with the sites of unsaturation resulting in the formation of an adduct of the triglyceride oil. The adduct formed is preferentially an anhydride and the substrate reacted in this manner with the triglyceride oil is preferably maleic anhydride. The term "maleation"
been historically applied to the reaction of natural unsaturated oils, fatty acids and their derivatives.
Functionaliztion of triglyceride oils by this method is well known in the art and is described in US
2,033,131, 2,033,132 and 2,063,540. These adducts are generally referred to in the literature as "maleated oils" or maleinized oils". The aqueous neutralization of these natural oil adducts is also well known in the art to produce soaps, emulsifiers and water-based lubricants.
The method described in co-pending application 13/776,542 involves the controlled non-aqueous neutralization of such adducts to provide thermoreversible ionomeric gels. As described in co-pending application 13/776,542 either an alkali or alkaline earth metal base may be employed
4 as the neutralization agent or an alkanolamine may be employed as a neutralization/esterification agent to produce the gels.
This method has proven to be applicable to a wide range of natural unsaturated oils and their derivatives and allows thermoreversible gels of any desired viscosity, from viscous liquids to hard solid gels, to be produced. As described' the method has many advantages over the prior art in that the gels are conveniently and economically produced and do not require the addition of expensive gelants or require the thermal "heat bodying" of the oil. The natural oils that may be used in the method of the present invention include any triglyceride oil that contains significant portions of unsaturated fatty acids. Natural triglyceride oils containing both non-conjugated and conjugated double bonds are suitable. Non-limiting examples of suitable triglyceride oils include soybean oil, linseed oil, safflower oil, sunflower oil, rapeseed oil, castor oil, tall oil, rosin oil and tung oil.
The following examples are intended to illustrate particularly exemplary Natural Oil Gels of the present invention and should not be construed to limit its scope or applicability in any way.
The following general method was used to prepare the Natural Oil Gels listed in Table 1.
In a first step, 2000g of the natural oil and the desired amount of maleic anhydride were charged to a 3 L four-neck round-bottom flask. The contents of the flask were gradually heated to 210 C with agitation under a nitrogen sparge. The reaction mixture was held at this temperature until no free maleic anhydride was detected in the reaction mixture by GC analysis. The reaction mixture was cooled to 50 C and an amount of Sodium Carbonate (0.25eq. per eq. maleic anhydride) was slowly added. The Sodium Carbonate could be added as a solid or as a water slurry.
The reaction mixture was held at 60 C until all of the Sodium Carbonate had reacted and the reaction mixture had cleared.
Excess water was stripped out under vacuum and the gel obtained was discharged. The gels obtained had exemplary properties, being clear and transparent and exhibited no oil bleed.
Table I.
Properties of Gelled Natural Oils IExam le I Percent Maleic Anhdride I Clarit I Oil Bleed I
Viscosit(cP) I
1) Soybean Oil 7.5 Transparent None 1000 2)Soybcan Oil 8 Transparent None 8000 3) Soybean Oil 9 Transparent None 5000 4) Soybean Oil 10 Transparent None 20000 )Soybean Oil 11 Transparent None Soft Gel (Slight Tack) 6) Soybean Oil 12 Transparent None Hard Gel (No tack) 6) Linseed Oil 7.5 Transparent None 5000 7)Linseed Oil 8 Transparent None 12000 8 )Linseed Oil 9 Transparent None 20000 9) Linseed Oil 10 Transparent None 80000 10)Linseed Oil 12 Transparent None Hard Gel (No tack) The viscosity of the gels in Examples 1-10 was controlled by the amount of maleic anhydride grafted on the fatty acid chains of the oil. Alternatively, the viscosity may also be controlled by the amount of neutralization of the maleic anhydride moieties as shown in Figure 1.
The following general method was used to prepare the natural oil gels listed in Table 2.
In a first step, 2000g of the natural oil and the desired amount of maleic anhydride were charged to a 3 L four-neck round-bottom flask. The contents of the flask were gradually heated to 210 C
with agitation under a nitrogen sparge. The reaction mixture was held at this temperature until no free maleic anhydride was detected in the reaction mixture by GC analysis. The reaction mixture was cooled to 50 C and triethanolamine or an alkoxylated triethanolamine (0.67 eq. per 1.0 eq. maleic anhydride) was slowly added. The reaction mixture was held at 80 C for I hour or until no unreacted maleic anhydride was observed in the Infrared Spectrum of the reaction mixture and the gel obtained was discharged.
Table 2.
Properties of Gelled Natural Oils Example Percent Maleic Anhydride Clarity Oil Bleed Viscosity( cP) 11) Soybean Oil 7.5 Transparent None 4500 12) Soybean Oil 8 Transparent None 8700 13) Soybean Oil 9 Transparent None 21000 14) Soybean Oil 10 Transparent None 46000 15) Soybean Oil 11 Transparent None Soft gel (slight Tack) 16) Soybean Oil 12 , Transparent None Hard Gel (No tack) 17) Linseed Oil 7.5 Transparent None 6200 18)Linseed Oil 8 Transparent None 9500 19)Linseed Oil 9 Transparent None 23000 20) Linseed Oil 10 Transparent None Soil Gel (Slight Tack) 21) Linseed Oil 12 Transparent None Hard Gel (No tack) Figure 2 shows the precise viscosity control of the vehicle that can be achieved by varying the percentage of the theoretical stoichiometric amount of triethanolamine added. A soybean oil/maleic anhydride adduct at 10.0 percent maleation was prepared as in examples 11-21. Triethanolamine was added from 20 percent to 70 percent of the theoretical stoichimetric amount required to react with all of the maleic anhydride moieties. The gels were discharged and viscosities were measured at 25 deg C. Above 70 percent theoretical Triethanolamine, hard gels were obtained.
Biodegradable Natural Oil Based Gelled Ink Vehicle Soybean oil gels of different viscosities as prepared in examples 1-10 and examples 11-21 were utilized as a carrier for the preparation of polytetrafluorethylene dispersions. Such dispersions are known in the art to be useful as additives in non-aqueous ink formulations to provide friction reduction and abrasion resistance to the final prints. The dispersions were prepared by mixing micronized PTFE into the gelled soybean oil at 80 C for 1 hour, allowing the mixtures to cool and then discharging. Dispersions were prepared at 25% and 75% PTFE
loading. Control dispersions were made using a standard soy based alkyd resin. The dispersions were then aged at 50 C in order to evaluate dispersion stability. The additives based on the soybean oil gels and the control alkyd were then formulated into a pigmented ink and prints were prepared. The prints were dried and then subjected to abrasion resistance testing. The results are shown in Table 3.
Table 3 Vehicle /Viscosity (cP) Percent PTFE Disnersion Stabilitvc Print Rub Resistance d 24) Soybean Oil Gel (9000 cP) 25 7 6 25) Soybean Oil Gel (9000 cP) 75 6 .. 6 26) Soybean Oil Gel (15000 cP) 25 8 8 27) Soybean Oil Gel (15000 cP) 75 7 .. 9 28) Soybean Oil Gel (20000 eP) 25 10 10 29) Soybean Oil Gel (20000 cP) 75 8 10 30) Soy based Alkyd (9000 cP) 25 4 4 31) Soy based Alkyd (9000 ell 75 4 4 c Dispersion Stability was evaluated by ageing samples at 50 deg C for 72 hours and monitoring the amount of PTFE that had settled. The dispersions were rated on a scale from 1-10. 1 being the worst stability and 10 the best.
d The rub resistance of the prints was rated on a scale from 1-10 with 1 being the worst rub resistance and 10 the best.
Clay Dispersions A soybean oil gel as prepared in Example 11 having a viscosity of 4500 cP was utilized as a carrier or dispersant for the preparation of stable dispersions of bentonite clay in soybean oil which are utilized as fillers in heat set inks. A soy based alkyd resin, commonly used in the industry, was used as a control or comparative example. As shown in Figure 3, clay loadings of up to 75 percent were achieved with a soybean oil gel of Example 11 while loadings of only 50 percent were achieved with the standard soy based alkyd resin.
The scope of the claims should not be limited by the preferred embodiments set forth in the examples, but should be given the broadest interpretation consistent with the description as a whole.
This method has proven to be applicable to a wide range of natural unsaturated oils and their derivatives and allows thermoreversible gels of any desired viscosity, from viscous liquids to hard solid gels, to be produced. As described' the method has many advantages over the prior art in that the gels are conveniently and economically produced and do not require the addition of expensive gelants or require the thermal "heat bodying" of the oil. The natural oils that may be used in the method of the present invention include any triglyceride oil that contains significant portions of unsaturated fatty acids. Natural triglyceride oils containing both non-conjugated and conjugated double bonds are suitable. Non-limiting examples of suitable triglyceride oils include soybean oil, linseed oil, safflower oil, sunflower oil, rapeseed oil, castor oil, tall oil, rosin oil and tung oil.
The following examples are intended to illustrate particularly exemplary Natural Oil Gels of the present invention and should not be construed to limit its scope or applicability in any way.
The following general method was used to prepare the Natural Oil Gels listed in Table 1.
In a first step, 2000g of the natural oil and the desired amount of maleic anhydride were charged to a 3 L four-neck round-bottom flask. The contents of the flask were gradually heated to 210 C with agitation under a nitrogen sparge. The reaction mixture was held at this temperature until no free maleic anhydride was detected in the reaction mixture by GC analysis. The reaction mixture was cooled to 50 C and an amount of Sodium Carbonate (0.25eq. per eq. maleic anhydride) was slowly added. The Sodium Carbonate could be added as a solid or as a water slurry.
The reaction mixture was held at 60 C until all of the Sodium Carbonate had reacted and the reaction mixture had cleared.
Excess water was stripped out under vacuum and the gel obtained was discharged. The gels obtained had exemplary properties, being clear and transparent and exhibited no oil bleed.
Table I.
Properties of Gelled Natural Oils IExam le I Percent Maleic Anhdride I Clarit I Oil Bleed I
Viscosit(cP) I
1) Soybean Oil 7.5 Transparent None 1000 2)Soybcan Oil 8 Transparent None 8000 3) Soybean Oil 9 Transparent None 5000 4) Soybean Oil 10 Transparent None 20000 )Soybean Oil 11 Transparent None Soft Gel (Slight Tack) 6) Soybean Oil 12 Transparent None Hard Gel (No tack) 6) Linseed Oil 7.5 Transparent None 5000 7)Linseed Oil 8 Transparent None 12000 8 )Linseed Oil 9 Transparent None 20000 9) Linseed Oil 10 Transparent None 80000 10)Linseed Oil 12 Transparent None Hard Gel (No tack) The viscosity of the gels in Examples 1-10 was controlled by the amount of maleic anhydride grafted on the fatty acid chains of the oil. Alternatively, the viscosity may also be controlled by the amount of neutralization of the maleic anhydride moieties as shown in Figure 1.
The following general method was used to prepare the natural oil gels listed in Table 2.
In a first step, 2000g of the natural oil and the desired amount of maleic anhydride were charged to a 3 L four-neck round-bottom flask. The contents of the flask were gradually heated to 210 C
with agitation under a nitrogen sparge. The reaction mixture was held at this temperature until no free maleic anhydride was detected in the reaction mixture by GC analysis. The reaction mixture was cooled to 50 C and triethanolamine or an alkoxylated triethanolamine (0.67 eq. per 1.0 eq. maleic anhydride) was slowly added. The reaction mixture was held at 80 C for I hour or until no unreacted maleic anhydride was observed in the Infrared Spectrum of the reaction mixture and the gel obtained was discharged.
Table 2.
Properties of Gelled Natural Oils Example Percent Maleic Anhydride Clarity Oil Bleed Viscosity( cP) 11) Soybean Oil 7.5 Transparent None 4500 12) Soybean Oil 8 Transparent None 8700 13) Soybean Oil 9 Transparent None 21000 14) Soybean Oil 10 Transparent None 46000 15) Soybean Oil 11 Transparent None Soft gel (slight Tack) 16) Soybean Oil 12 , Transparent None Hard Gel (No tack) 17) Linseed Oil 7.5 Transparent None 6200 18)Linseed Oil 8 Transparent None 9500 19)Linseed Oil 9 Transparent None 23000 20) Linseed Oil 10 Transparent None Soil Gel (Slight Tack) 21) Linseed Oil 12 Transparent None Hard Gel (No tack) Figure 2 shows the precise viscosity control of the vehicle that can be achieved by varying the percentage of the theoretical stoichiometric amount of triethanolamine added. A soybean oil/maleic anhydride adduct at 10.0 percent maleation was prepared as in examples 11-21. Triethanolamine was added from 20 percent to 70 percent of the theoretical stoichimetric amount required to react with all of the maleic anhydride moieties. The gels were discharged and viscosities were measured at 25 deg C. Above 70 percent theoretical Triethanolamine, hard gels were obtained.
Biodegradable Natural Oil Based Gelled Ink Vehicle Soybean oil gels of different viscosities as prepared in examples 1-10 and examples 11-21 were utilized as a carrier for the preparation of polytetrafluorethylene dispersions. Such dispersions are known in the art to be useful as additives in non-aqueous ink formulations to provide friction reduction and abrasion resistance to the final prints. The dispersions were prepared by mixing micronized PTFE into the gelled soybean oil at 80 C for 1 hour, allowing the mixtures to cool and then discharging. Dispersions were prepared at 25% and 75% PTFE
loading. Control dispersions were made using a standard soy based alkyd resin. The dispersions were then aged at 50 C in order to evaluate dispersion stability. The additives based on the soybean oil gels and the control alkyd were then formulated into a pigmented ink and prints were prepared. The prints were dried and then subjected to abrasion resistance testing. The results are shown in Table 3.
Table 3 Vehicle /Viscosity (cP) Percent PTFE Disnersion Stabilitvc Print Rub Resistance d 24) Soybean Oil Gel (9000 cP) 25 7 6 25) Soybean Oil Gel (9000 cP) 75 6 .. 6 26) Soybean Oil Gel (15000 cP) 25 8 8 27) Soybean Oil Gel (15000 cP) 75 7 .. 9 28) Soybean Oil Gel (20000 eP) 25 10 10 29) Soybean Oil Gel (20000 cP) 75 8 10 30) Soy based Alkyd (9000 cP) 25 4 4 31) Soy based Alkyd (9000 ell 75 4 4 c Dispersion Stability was evaluated by ageing samples at 50 deg C for 72 hours and monitoring the amount of PTFE that had settled. The dispersions were rated on a scale from 1-10. 1 being the worst stability and 10 the best.
d The rub resistance of the prints was rated on a scale from 1-10 with 1 being the worst rub resistance and 10 the best.
Clay Dispersions A soybean oil gel as prepared in Example 11 having a viscosity of 4500 cP was utilized as a carrier or dispersant for the preparation of stable dispersions of bentonite clay in soybean oil which are utilized as fillers in heat set inks. A soy based alkyd resin, commonly used in the industry, was used as a control or comparative example. As shown in Figure 3, clay loadings of up to 75 percent were achieved with a soybean oil gel of Example 11 while loadings of only 50 percent were achieved with the standard soy based alkyd resin.
The scope of the claims should not be limited by the preferred embodiments set forth in the examples, but should be given the broadest interpretation consistent with the description as a whole.
Claims (4)
1. A non-aqueous ink formulation comprising a polytetrafluoroethylene dispersion comprising a gelled printing vehicle for heat-set or other lithographic printing, the vehicle comprising an adduct derived from the reaction product of a natural unsaturated triglyceride oil, or derivative with a substrate suitable for Diets Alder reaction or Ene reaction and wherein said adduct is reacted in a non-aqueous neutralization reaction with a suitable base to form an ionomeric anhydrous gel.
2. The non-aqueous ink formulation of claim 1, wherein the base is an alkanolamine.
3. The non-aqueous ink formulation of claim 1 or 2, wherein the gelled printing vehicle is used as carrier or vehicle for additives in the non-aqueous ink formulation.
4. The non-aqueous ink formulation of claim 1 or 2, wherein the gelled printing vehicle is used as dispersant for additives in the non-aqueous ink formulation.
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US201261603251P | 2012-02-25 | 2012-02-25 | |
US61/603,251 | 2012-02-25 | ||
US13/776,681 US20140243550A1 (en) | 2013-02-25 | 2013-02-25 | Natural oil derived gelled ink vehicles |
US13/776,681 | 2013-02-25 | ||
PCT/US2013/027705 WO2013126922A1 (en) | 2012-02-25 | 2013-02-25 | Natural oil derived gelled ink vehicles |
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JP (1) | JP6188730B2 (en) |
CA (1) | CA2865433C (en) |
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US3412053A (en) * | 1964-07-06 | 1968-11-19 | Huber Corp J M | Printing inks and varnishes |
DE2264467C3 (en) * | 1971-06-25 | 1978-08-24 | Nippon Zeon Co., Ltd., Tokio | Water-dilutable paint composition made from the neutralized reaction product of an unsaturated carboxylic acid or its anhydride with polydienes |
SU445688A1 (en) * | 1972-09-18 | 1974-10-05 | Ивановский Химико-Технологический Институт | Method for producing modified castor oil |
JPH064799B2 (en) * | 1987-03-31 | 1994-01-19 | 谷口インキ製造株式会社 | Printing 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 |
ES2152549T3 (en) * | 1995-08-11 | 2001-02-01 | Henkel Kgaa | POLYSTYRENE BINDERS. |
CN101563430B (en) * | 2006-11-03 | 2013-10-30 | 太阳化学公司 | Stable offset emulsion inks containing water tolerant emulsion stabilizer |
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