Flexographic printing process with wet on wet capability

Inactive Publication Date: 2011-10-13
TECHNOSOLUTIONS ASSESSORIA
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AI-Extracted Technical Summary

Problems solved by technology

The controlled gel results from formation of a polymer chain network, or polymer segment...
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Method used

[0068]This invention analyses what can be defined as reverse solvency, controlling or changing the Hansen Solubility Parameter of the medium in such way as to get some modified degree of solvency or solvation of the chosen polymer to produce a gel, or solid-like, layer of ink having enough strength and rigidity to support a flexographic overprint process or a letterpress printing process.
[0071]The high mobility of the reactive components during the cure process in the gel, and after the gel is broken as the temperature increases in the curing phase, assures the highest degree of chemical conversion without any additional control or apparatus.
[0080]The reference 4, on FIG. 10, presents a different inking system in the absence of conventional ink tray, replaced by a system similar to that used in the field of solventless laminators, where the gelled ink reservoir (4.3) supplied automatically or manually by feeding system (4.2) is formed by a low speed metering roll (4.1) and medium speed metering roll (4.4) that apply a sufficient amount of ink to completely cover the anilox roll (4.6) cleaned from this excess of ink by the blade (4.5) to be applied as a very thin layer over the printing plate attached to the plate cylinder (4.7) and then finally transferred to the substrate. As in the other examples, the contention can (4.8) must be applied to prevent color contamination in case of ink spilling.
[0094]If the ink still using solvent in the formulation, the invention provides at least two great improvements over traditional solvent flexographic inks:[0095]very strong inks with a viscosity below 2.500 cps are easily achieved due to a characteristic of selected monomers and oligomers which are able to print in a wet on wet basis and exhibit a high load pigment capacity;[0096]the inks obtained can show a reduced VOLATILE ORGANIC COMPOUNDS, even below 15% of total formula, in comparison with formulation inks from prior art having high solids solvents that use about 50% of VOLATILE ORGANIC COMPOUNDS in their composition.
[0097]The combination of those two characteristics—very strong color inks and low VOLATILE ORGANIC COMPOUNDS—gives an ink the capability to meet the European and American VOLATILE ORGANIC COMPOUNDS and pollution regulations, without any pre or final treatment in the air or residues. These measures reduce the cost of final products, improve the ink quality and contribute to the environmental preservation.
[0098]If a solvent are added into the ink composition, the main criteria to choose the solvent can be summarized as follows:[0099]a) The selected solvent must show stability in the medium (e.g. avoid Alcohols and Glycols that could undergo transesterification in a short period of time, generating toxic acrylates).[0100]b) A nonreactive solvent useful in this invention should be chosen from those that are the most human friendly as possible, with low skin and respiratory irritation, and also being compatible with the final destination of the ink (Flexible food packaging, for instance).[0101]c) In order to minimize the amount of nonreactive solvent added, preferred choices will have Hansen Solubility Parameters as far as possible from the Hansen Solubility Parameters of the final formulated mixture. The Hansen Solubility Parameters of mixtures are calculated from weight (or volume) averaging of the Hansen Solubility Parameters of the individual components. The effect of a given component on this average is greater at the same concentration when its Hansen Solubility Parameters are further from the final average. This provides the potential for greatly reduced levels of nonreactive solvent.[0102]d) The Hansen Solubility Parameters and concentration of any nonreactive solvent that may be present must lead to a final position on the Hansen Solubility charts, such as those shown in FIGS. 1, 2, and 7, that is just within the region defined by the polymer radius of solubility. Its evaporation will then lead to the desired gel formation, since the Hansen Solubility Parameters of the liquid remaining are then moved to just outside the boundary defining the solubility of the polymer. This leads to the gel formation as above disclosed.[0103]e) In Hansen Solubility Parameter diagrams such as those shown in FIGS. 1, 2, and 7, the line connecting the averaged Hansen Solubility Parameters of the liquids in the formulated ink and the Hansen Solubility Parameters of any chosen solvent in the formulation should preferably pass through the polymer center of solubility since this is the most sensitive point for efficient gel destruction resulting in a low viscosity flexographic applicable ink with less than 4000 cps and preferably less than 2500 cps and mostly preferably less than 1000 cps of the formulation.[0104]f) The boiling point of any chosen nonreactive solvent that may be in the formulation is preferably lower than the boiling point of any of the monomers present in order to assure its evaporation without any noticeable loss of monomers.
[0106]Following the established criteria for selection of the right nonreactive solvents for practice of the present invention, preferred solvents include, but are not limited to: Propylene Glycol Monomethyl Ether, Dipropylene Glycol Monomethyl Ether, Propylene Glycol Monomethyl Ether Acetate, n-Propyl Propionate, n-Butyl Propionate, n-Pentyl Propionate, Propylene Glycol Diacetate, Diethyl Carbonate, and Dimethyl Carbonate. The use of nonreactive solvents having medium to low relative evaporation rates such as propylene glycol monomethyl ether or dipropylene glycol monomethyl ether also improve the ink stability in the machine allowing up to 72 hours of printing without any interference of operators to adjust the viscosity. This means the standard of impression also remains constant during this time which, in turn, means a very desirable, stable flexographic printing process.
[0112]Known organic gellants that are suitable to turn a VOLATILE ORGANIC COMPOUNDS free radiation curable printing ink into a gel at room temperature said gel being easily destroyable by means of temperature, agitation, or combination of both, creates a possibility to produce a system and the right ink formulations to overcome the limitations that still obligate the formulas to contain a non reactive diluents to the wet on wet printing process in flexography and at the same time avoid the use of high viscosity inks in letterpress that demands more pressure and exhibits more difficulties to print.
[0141]The criteria to select the monomers can be summarized by the fol...
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Benefits of technology

[0019]It is an object of this invention to provide a flexographic printing system and process with the overprint color process without solvent or with a reduced...
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Abstract

The invention refers to a flexographic printing process with wet on wet capability based on controlled polymer or polymer segment precipitation that leads to gel formation of ink compounds by controlling the solubility parameter of the ink system. The mechanism to obtain a desirable wet on wet color trapping is the formation and/or presence of a gel in the applied ink film due to a controlled physicochemical mechanism of resin precipitation. This is accomplished either by controlling a change in the Hansen Solubility Parameter of the liquid in the ink through evaporation of some or all of a non-reactive and volatile solvent, or alternatively by use of a polymer comprised of two distinct and separate segments one of which is soluble in the monomer/oligomer mix and the other of which is not. The insoluble segments form a reversible gel that is broken to a liquid by shear in the application process, allowing application of a liquid ink, and is reestablished in the applied ink film in such a manner and with such strength as to allow overprinting in the wet on wet flexographic printing process.

Application Domain

Technology Topic

SolubilityHansen solubility parameter +11

Image

  • Flexographic printing process with wet on wet capability
  • Flexographic printing process with wet on wet capability
  • Flexographic printing process with wet on wet capability

Examples

  • Experimental program(3)

Example

Example 1
Ink with Small Amount of Solvent
[0184]Formula A is for an EB curable ink formulated according to the present invention for a non-food application that contains only 5% solvent and 0.5% of Polymer (Polyvinyl Butyral-Butvar® B76): Formula A is showed on Table 4 below.
TABLE 4 ink with small amount of solvent FORMULA A Product Trade Name Supplier Yellow Magenta Cyan Black Additive Omnistab 510 IGM Resins 0.5 0.5 0.5 0.5 Additive Tego Glide 432 Tego Chemie 1.0 1.0 1.0 1.0 Additive Tego Dispers 685 Tego Chemie 4.0 2.5 — — Additive Disperbyk 168 Altana 3.0 5.5 6.5 5.0 Monomer TMPTA Cytec 51.0 51.0 51.0 48.5 Monomer HDDA Cytec 5.0 5.0 5.0 4.5 Epoxidized Soy CN111 Sartomer 5.5 6.0 6.0 6.0 Bean Oil Acrylate Additive Solsperse 22000 Noveon 2.0 — — — Additive Solsperse 5000 Noveon — — 1.5 2.0 Yellow Pigment Irgalite Yellow LCT CIBA 22.5 — — — Magenta Pigment Permanent Rubine L4B 01 Clariant — 23.0 — — Cyan Pigment Heliogen LBL 7081D BASF — — 23.0 — Black Pigment Special Black 250 Degussa — — — 27.0 Polymer Butvar B76 Solutia 0.5 0.5 0.5 0.5 Solvent Dowanol PM Dow 5.0 5.0 5.0 5.0 Viscosity (cps) 1500 1750 1350 2100 Color Density Anilox: 480 l/cm - 1.85 cm3/m2 1.12 1.35 1.89 1.66
[0185]The production was carried out in a Comexi FW 1508 at a production speed of 350 m/min using only cold air in the interstation drying devices, and cured at 20 kGy in an EZCure-I DF™ produced by ESI (Energy Sciences Inc.—Wilmington, Mass.).
[0186]The printed material was tested according to the scotch test method in adhesion and the results are given in the Table 5 below:
TABLE 5 Results from printed materials Printed Treatment Scotch Material Level1 Test2 1- Clear polypropylene 40 passed 2- Pearlized polypropylene 40 passed 3- Clear polyethylene 38 passed 4- White polyethylene 38 passed 1Corona treatment 2Scotch ® 880
[0187]The present formulation shows the following trapping values, where the Achieved values, obtained through the invention, are compared to minimum values obtained according to known offset method.
Achieved Web Offset (min) Red: 75% 65% Green: 67% 75% Blue: 50% 70%
[0188]It is clear that gel strength achieved in the above formulation was not sufficient to ensure a minimum desirable trapping value for all colors, even if some colors achieve a little more than the minimum, it shows the inconsistency and potential problems that can occur during the printing runs.
[0189]In order to evaluate the formulation above, all variations on the Hansen Solubility Parameter before and after a solvent loss of 5% of the formulation was calculated in the following Table 6 and the following formula A was developed:
TABLE 6 Hansen Solubility Parameter FORMULA A - GENERAL PURPOSE MONOMERS (NOT FDA APPROVED) INITIAL FORMULA (A1) FINAL FORMULA (A2)* δh δp δh δp Compound A1 (J/cm3)1/2 (J/cm3)1/2 A2 ((J/cm3)1/2 (J/cm3)1/2 TMPTA 83.6% 7.524 12.54 91% 8.19 13.65 HDDA 8.2% 0.9676 0.9184 9% 1.062 1.008 TRPGDA 0% — — 0% — — Dowanol PM 8.2% 1.1152 0.5904 0% — — Total 100% 9.6068 14.0488 100% 9.252 14.658 *After all solvent evaporation
[0190]After removing all other components of the formulation, and restricting the formula to the compounds which will form the solubilization medium, formula A gives the A1 liquid compound formula, where TMPTA represents 83.6%, HDDA is equal to 8.25% and the 5% solvents in the total formula becomes 8.2% of the liquid medium.
[0191]The Hansen Solubility Parameter variation of the initial Formula A1 (before solvent evaporation) and Formula A2 (after solvent evaporation) is given below:
δh ((J/cm3)1/2 δp (J/cm3)1/2 Formula A1 9.6 14.0 Formula A2 9.3 14.7
[0192]Due to insufficient trapping in previous example, a behavior of the gel is well studied and hardness was defined as one of the properties that best represent the gel itself.
[0193]To provide the readings of the gel hardness, formulations with 5%, 4%, 3%, 2% 1% of polyvinyl butyral (Butvar B76) by weight of the total non volatile was prepared for each basic colors (yellow, Magenta, cyan and Black) and measured by means of a Shore 00 Durometer following the ASTM D2240-05 “Standard Test Method for Rubber Property” produced by Woltest Company—Rua Francesco Mosto, 55-Sāo Paulo-05220-005-SP-Brazil. This test method is based on the penetration of a specific type of indentor when forced into the material under specified conditions; it is an empirical test.
[0194]A 150 g of total formula was produced for each color and concentration and gelified in a can to leave the surface free and flat to apply the Shore 00 Durometer reading head and obtain the correct measure.
[0195]This kind of Durometer is normally used to measure very soft polymeric foams, such as polyurethane foam used in pillows and mattress and the right reading is considered the reading obtained when the values have stabilized in a sequence of at least 3 consecutive readings. The test is carried out on the gel after evaporation of enough amount of the solvent, in order to change the Hansen solubility parameter and allow the gellification of the ink for the cases where the solvent is present in the formulation to adjust the Hansen solubility parameter or after enough time in the cases of solvent free formulation.
Hardness is read after 15 minutes from the constant weight of the sample, which means the sample lose practically all solvent and reach the highest hardness of the gelled ink.
[0196]It was found that this possibility of reading the gel hardness is a very important physical difference between the invention inks and the known inks that are based on viscosity increase upon solvent evaporation. In fact all attempts to read very high viscosity offset inks failed for all types of color because even when a hardness value was detected in a first reading, the sequence of reading does not stabilize, decreasing each time it is repeated to a point when the reading was no longer possible to be done, because the Durometer sank in the viscous ink. This is due to the fact that a viscous ink does not establish a gelated base for the readings.
[0197]The readings in the gel hardness in FIG. 12 explain quite well the results achieved, where only the yellow ink had enough consistency to support the overprinting process. In fact it was found that gel hardness is also depending on the type of pigment used; the same composition may provide a gel having sufficient hardness when yellow pigment is used and a gel not hard enough when black pigment is used, as discussed in the following.
[0198]When the composition of Formula A was modified to include a greater amount of polymer, the trapping values improved dramatically as shown in following example 2.
[0199]The gel hardness vs. gellant concentration for Polyvinyl Butyral (Butvar B76) is reasonably linear for the selected percentage interval but when hardness decreases below 5-6 shore 00 it is impossible to read it since the gel texture and consistence cannot support the measurement device that tends to sink in the ink. It was found by carrying out empirical tests that below this lower limit value, i.e. 4 Shore 00, the gel strength can no longer support the flexographic overprinting process.
[0200]The different behavior of the black inks can be explained as follows. Typical carbon black pigments have Hansen solubility parameters such that they readily adsorb common solvents and/or polymers. This can easily affect the Hansen solubility parameters of the liquid phase in the inks. The absorption of polymers, in particular, leads to a rapid increase in viscosity, since the molecular weight of the carbon black, with say two polymer molecules adsorbed is approximately twice that of the individual polymer molecules. The effect on the viscosity of doubling the molecular weight is greater than that of the two individual polymer molecules.
[0201]Data for the most conventional carbon blacks gives the following Hansen solubility parameters to the carbon black: δP: 6 (Mpa3)1/2 and δH 5,5(Mpa3)1/2, bringing the total Hansen solubility parameter to inside of the solubility performance of Polyvinyl Butyral (Butvar B76).
[0202]As the use of the black in all printing tests was programmed to be the last printed color, the results were not affected by the insufficient gel hardness. To overcome the trapping problems of the first formulation and taking the information achieved from the hardness evaluation, a new formula was prepared with 2.5% Polyvinil Butyral in all colors as following:

Example

Example 2
Ink with Increased Amount of Polymer
[0203]In example 2, the amount of polymer was increased, that means a elevation in the polymer network density and in the amount of change in the Hansen Solubility Parameter, in order to ensure a sufficient distance between the liquid and gel state, avoiding ink gelation in the inking system. Table 7 shows Formula B.
TABLE 7 FORMULA B Product Trade Name Supplier Quantity Additive Omnistab 510 IGM Resins 0.5 0.5 0.5 0.5 Additive Tego Glide 432 Tego Chemie 1.0 1.0 1.0 1.0 Additive Tego Dispers 685 Tego Chemie 4.0 2.5 — — Additive Disperbyk 168 Altana 3.0 5.5 6.5 5.0 Monomer TMPTA Cytec 46.5 46.5 46.5 44.0 Monomer HDDA Cytec 3.0 3.0 3.0 2.5 Epoxidized Soy CN111 Sartomer 5.5 6.0 6.0 6.0 Bean Oil Acrylate Additive Solsperse 22000 Noveon 2.0 — — — Additive Solsperse 5000 Noveon — — 1.5 2.0 Yellow Pigment Irgalite Yellow LCT CIBA 22.5 — — — Magenta Pigment Permanent Rubine L4B 01 Clariant — 23.0 — — Cyan Pigment Heliogen LBL 7081D BASF — — 23.0 — Black Pigment Special Black 250 Degussa — — — 27.0 Polymer Butvar B76 Solutia 2.0 2.0 2.0 2.0 Solvent Dowanol PM Dow 10.0 10.0 10.0 10.0 Viscosity (cps) 1250 1600 1250 1900 Density Anilox: 480 l/cm - 1.85 cm3/m2 0.97 1.32 1.79 1.47
[0204]The production was done in a Comexi FW 1508 at a production speed of 350 m/min using only cold air in the interstation drying devices and cured at 20 kGy in an EZCure-I DF™ produced by ESI (Energy Sciences Inc.—Wilmington, Mass.).
[0205]The printed material was tested in adhesion and the results are given in the Table 8 below:
TABLE 8 Results from printed materials Printed Treatment Scotch Material Level1 Test2 1- Clear polypropylene 40 Passed 2- Pearlized polypropylene 40 Passed 3- Clear polyethylene 38 Passed 4- White polyethylene 38 Passed 1Corona treatment 2Scotch ® 880
[0206]The main variation from the previous formula and this one (Formula B) is increasing the amount of polymer (Polyvinyl Butyral-Butvar® B76) from 0.5 to 2.0% and the amount of solvent from 5% to 10%.
[0207]It was clear when the new formulation was studied that the amount of the nonreactive solvent was not enough in the formula A to move the Hansen Solubility Parameter of the final liquid mixture to a point sufficiently inside the solubility region of the PVB to ensure the right solubilization. This was not so clear in the first formula due to the amount of PVB in the formula.
[0208]The level of solvent needed to adjust to a minimum level of solubilization was recalculated to 17% of the liquid compound (10% of the total Formula B) instead of 8.2% of the liquid formulation or 5% of the total formula of the Formula A. The Table 9 below gives the new situation for the Hansen Solubility Parameters for the Formula B1 (before solvent evaporation) and B2 (after solvent evaporation):
TABLE 9 Hansen Solubility Parameters for the Formulae B1 and B2 FORMULA B - GENERAL PURPOSE MONOMERS (NOT FDA APPROVED) INITIAL FORMULA (B1) FINAL FORMULA (B2)* δh δp δh δp Compound B1 ((J/cm3)1/2 (J/cm3)1/2 B2 ((J/cm3)1/2 (J/cm3)1/2 TMPTA 78.0% 7.02 11.7 93.9% 8.451 14.085 HDDA 5.0% 0.59 0.56 6.1% 0.7198 0.6832 TRPGDA 0% — — 0% — — Dowanol PM 17.0% 1.734 0.697 0% — — Total 100% 9.922 13.484 100% 9.1708 14.7682
[0209]The trapping results here are much improved as seen by the following values:
Achieved Web Offset (min) Red: 89% 65% Green: 84% 75% Blue: 81% 70%
[0210]As the above data shows, the trapping values exceed by a good margin the minimum desirable trapping and also showed great stability during to the printing run, even with a lot of stop and go operations. This is the worst scenario for testing trapping stability.
[0211]The Hansen Solubility Parameters in the Formula B1 show a good solvency for the polymer (PVB) ensuring a right solubilization with no noticeable tendency to gel formation. After the solvent evaporation, even with use only of cold air and up to 350 m/min in a Comexi FW 1508, the trapping values were considered very acceptable and stable. The changes in the Hansen Solubility parameters are given below:
δh ((J/cm3)1/2 δp (J/cm3)1/2 Formula B1 9.9 13.5 Formula B2 9.2 14.8

Example

Example 3
Composition Approved for Food Packing
[0212]Using the same general formulation principle, but using only FDA approved monomer for Food Packing, the previous formulations is changed by exchanging HDDA with TRPGDA (Tripropylene Glycol Diacrylate).
[0213]In both case, the use of HDDA and/or TRPGDA is directed to bring the TMPTA as close as possible to the solubility border of Butvar® B76 in order to reduce as much as possible the Methoxy Propanol (Dowanol PM) level in the ink, since after its evaporation there is an adverse effect of VOLATILE ORGANIC COMPOUNDS in the atmosphere. Table 10 below shows formula C:
TABLE 10 gelled ink with small amount of solvent FORMULA C Product Trade Name Supplier Quantity Additive Omnistab 510 IGM Resins 0.5 0.5 0.5 0.5 Additive Tego Glide 432 Tego Chemie 1.0 1.0 1.0 1.0 Additive Tego Dispers 685 Tego Chemie 4.0 2.5 — — Additive Disperbyk 168 Altana 3.0 5.5 6.5 5.0 Monomer TMPTA Cytec 37.5 37.5 37.5 36.5 Monomer TRPGDA Cytec 12.0 12.0 12.0 11.0 Epoxidized Soy CN111 Sartomer 5.5 6.0 6.0 6.0 Bean Oil Acrylate Additive Solsperse 22000 Noveon 2.0 — — — Additive Solsperse 5000 Noveon — — 1.5 2.0 Yellow Pigment Irgalite Yellow LCT CIBA 22.5 — — — Magenta Pigment Permanent Rubine L4B 01 Clariant — 23.0 — — Cyan Pigment Heliogen LBL 7081D BASF — — 23.0 — Black Pigment Special Black 250 Degussa — — — 27.0 Polymer Butvar B76 Solutia 2.0 2.0 2.0 2.0 Solvent Dowanol PM Dow 10.0 10.0 10.0 9.0 Viscosity (cps) 1370 1640 1280 2100 Density Anilox: 480 l/cm - 1.85 cm3/m2 0.93 1.29 1.47 1.37
[0214]The production was carried in a Comexi FW 1508 with a production speed of 350 m/min using only cold air in the interstation drying devices and cured at 20 kGy in an EZCure-I DF™ produced by ESI (Energy Sciences Inc.—Wilmington, Mass.).
[0215]The printed material was tested for adhesion with the results being given in the Table 11 below:
TABLE 11 Results from printed material Printed Treatment Scotch Material Level1 Test2 1- Clear polypropylene 40 passed 2- Pearlized polypropylene 40 passed 3- Clear polyethylene 38 passed 4- White polyethylene 38 passed 1Corona treatment 2Fita Scotch ® 880
[0216]Proceeding to the Hansen Solubility Parameter evaluation, the Table 12 below shows the change in these before and after solvent evaporation:
TABLE 12 Changes in the Hansen Solubility Parameter FORMULA C - MONOMERS FDA APPROVED FOR FOOD PACKAGING INITIAL FORMULA (C1) FINAL FORMULA (C2)* δh δp δh δp Compound C1 ((J/cm3)1/2 (J/cm3)1/2 C2 ((J/cm3)1/2 (J/cm3)1/2 TMPTA 63.0% 5.67 9.45 75.9% 6.831 11.385 HDDA 0.0% 0 0 0.0% 0 0 TRPGDA 20.0% 2 2.7 24.1% 2.41 3.2535 Dowanol PM 17.0% 2.312 1.224 0.0% 0 0 Total 100% 9.982 13.374 100% 9.241 14.6385 C1 are the Hansen solubility parameters before solvent evaporation and C2 are the Hansen solubility parameters after solvent evaporation.
[0217]Changes in the Hansen Solubility parameters are indicated below:
δh ((J/cm3)1/2 δp (J/cm3)1/2 Formula C1 10.0 13.4 Formula C2 9.2 14.6
[0218]The trapping behavior that was achieved was also good enough for flexographic printing process as presented in the following results:
Achieved Web Offset (min) Red: 99% 65% Green: 96% 75% Blue: 95% 70%
[0219]Based on the concept described in the present invention many formula variations of the kind described here may be implemented by formulators skilled in the art. There are a large number of choices regarding non-reactive solvents, solvent-soluble resins, monomers and oligomers that would allow compliance with the claims of this invention. Also, the Hansen Solubility Parameters for many other monomers and oligomers are not currently known. Such data would help develop ink formulations within the scope of this invention without requiring numerous trials.
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PUM

PropertyMeasurementUnit
Temperature15.0°C
Temperature35.0°C
Fraction0.0fraction
tensileMPa
Particle sizePa
strength10

Description & Claims & Application Information

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