WO1988000961A1

WO1988000961A1 - Improvements in or relating to printing

Info

Publication number: WO1988000961A1
Application number: PCT/GB1987/000540
Authority: WO
Inventors: Richard Frederick Small; Lascelle Augustus Barrow; Barry Martin Dix; Dakshesh Shashikant Patel
Original assignee: Small Products Limited
Priority date: 1986-07-30
Filing date: 1987-07-30
Publication date: 1988-02-11
Also published as: AU608532B2; AU7780287A; DK169388D0; JPH01503391A; FI890430A0; ES2004959A6; DK169388A; GR871218B; FI890430A; EP0296176A1

Abstract

A water based screen printing ink that is at least partially curable by irradiation and comprises an emulsion of a resin dispersed in water.

Description

IMPROVEMENTS IN OR RELATING TO PRINTING

This invention relates to printing and in particular to screen printing (commonly known as silk screen printing). As is well known, the silk screen printing process involves the use of a screen of silk, polyester, nylon, metal gauze or any other suitable mesh-like or perforated material. For convenience (and for consistency with the terminology historically employed in this art) the term "silk screen printing" will be used herein and it will be appreciated that no restriction to "silk" material is thereby intended.

Although silk screen printing is a very old technique, it still has numerous problems and/or limitations associated with it. For example, where several large-size multi-colour sheets are to be silk screen printed for, say, a poster to be pasted up on a hoarding, large quantities of specialised, screen printing inks are needed which are expensive.

The printing inks required for screen printing are quite different from those to be used for other forms of printing. The screen printing inks being generally used at present are organic solvent-based and usually contain ethyl or nitro cellulose resins. They are dried in warm air tunnels by driving off the organic solvents, and are thus potentially hazardous to the printing operatives. Another problem which arises with such organic solvent-based screen printing inks, relates to solvent loss from the ink on the printing screen whereby the ink increases in viscosity and after a certain period of time will not properly pass through the open areas of the printing mesh. This "drying in" results in loss of printed image and is described as screen stability, i.e. inks with poor screen stability "dry in" rapidly.

Recent developments over the last ten years have seen the introduction of Ultra-Violet-curing screen process inks. Here the formulations use raw materials which do not increase in their viscosity on the printing screen but instead dry by exposure to intense Ultra Violet light. This means that this type of ink has almost unlimited screen stability compared to non-UV curing, organic solvent-based, screen printing inks. However, such UV-curing inks are expensive, and leave a very thick print coat on the paper surface - particularly where multi-colour, e.g. 4-colour, silk screen printing is effected.

Such thick or heavy print images on the surface of a sheet of poster paper often necessitate that for mounting the poster to its hoarding, a special adhesive - which is other than an inexpensive starch-based adhesive - must be used if efficient bonding is to be achieved. A similar problem often arises with the older type of organic solvent-based silk screen printing inks. This adhesion problem is common where the individual sheets overlap, e.g. at overlapping marginal edges of adjacent poster sheets. The back of the top sheet does not have sufficient adhesion to the ink surface printed on the sheet beneath. When the poster paste dries out, the top sheet of the overlap often curls up and away from the sheet underneath. The problem is particularly severe when the paper is completely covered with several layers of ink. Posters printed with offset litho inks have less tendency to curl when they dry out compared to those produced with screen printing inks. As the screen printing process achieves its high quality print appearance by a much higher ink deposit, the curl problem is pronounced with screen printing inks. Therefore the adhesives used with screen printed posters need to have better adhesion properties to prevent overlap curl.

Mixtures of one or more starch adhesives and one or more polyvinyl alchol (P.V.A.) adhesives were investigated by the applicants, and these were found to give a much improved adhesion at the overlapping edges of superimposed sheets as compared to a 100% starch-based adhesive product. However, mixtures of starch and P.V.A. adhesives have the disadvantage of being more expensive and the resultant improved adhesion makes the removal of the total poster from the hoarding more difficult. Thus they are not likely to find favour with bill-posters, i.e. those responsible for puting up the posters on the hoardings.

It is therefore considered desirable to reduce, if not wholly obviate, some or all of the above-mentioned and/or other disadvantages associated with or relating to prior art screen printing methods and inks.

According to this invention there is provided a printing ink for silk screen printing, characterised in that the screen printing ink is a water-based ink that is at least partially curable by irradiation and comprises an emulsion of a resin dispersed in water.

The term "irradiation" as used herein in relation to curing refers to eloctro-magnetic radiations having wavelengths shorter than those of the visible spectrum, and the term thus includes UV (ultra-violet) and electron beam radiations.

Preferably the emulsion has said resin wholly (or at least substantially) in dispersed phase and wholly (or at least substantially) insoluble in the water, the water being the continuous phase of the emulsion.

Advantageously , said resin comprises 30% to 60% ( preferably 50% ) of the emulsion.

Preferably said resin comprises an unsaturated acrylate resin, e.g. polyester acrylate resin. It is envisaged that an epoxy acrylate resin and/or a urethane acrylate resin might additionally or alternatively be employed. Preferably the water-based screen printing ink has a composition which comprises one or more photoinitiators and is at least partially curable by irradiation comprising electromagnetic radiations in the ultra-violet light waveband.

Alternatively, or additionally, the screen printing ink may be at least partially curable by irradiation with an electron beam.

Where the screen printing ink is curable solely by irradiation with an electron beam, then photoinitiator(s) may be omitted from the printing ink composition.

Preferably, and in either case, the water-based printing ink composition is subjected to heat or to thermal radiation, e.g. is subjected to electromagnetic radiations in the infra-red light waveband, prior to curing.

The following relates to the production of individual silk screen printed sheets and their treatment for application onto hoarding sites in accord with embodiments of the present invention. As well as single sheet posters, the embodiments are concerned with the usual combinations of multiple sheet posters (e.g. "16 sheet", "48 sheet" or "96 sheet" posters) for pasting up onto large hoardings. The screen printing method used in these embodiments may be for the production of four colour halftone prints as well as continuous line and tone colour prints.

The following embodiments of this invention concern the screen printing ink used to print the sheets. The screen printing ink in each of these embodiments comprises an emulsion of a resin dispersed in water, i.e. is water miscible, and dries by exposure to Ultra Violet radiation. The emulsion has said resin wholly (or at least substantially) in dispersed phase and wholly (or at least substantially) insoluble in the water, the water being the continuous phase of the emulsion. Thus the screen printing ink contains water and is water thinnable to a considerable extent, but the water is to be regarded as a carrier or diluent (rendering the ink aqueously reducible in viscosity) rather than as a solvent. Preferably the water-based screen ink contains at least 40% water.

In a first embodiment of this invention the printing ink comoosition comprises: an Ultra Violet curing resin emulsified with water, e.g. an equal part of water; a photoinitiator and an aqueous pigment dispersion. In the emulsion the water is the continuous phase and the resin (amounting to 50% of the emulsion) is the dispersed phase. One specific formulation of this is given in Example 1.

Example 1 Parts by weight

Emulsion Laromer* PE 55W^{(1 )} 95.3 Darocur* 1173⁽²⁾ Photoinitiator 2.0

Aquadisperse* Phthalo Blue GB EP⁽³⁾ 2.7

A composition as formulated in Example 1 was printed through a screen made from 165 threads per cm polyester mesh halfcalendered. The calendered side was positioned face down towards the substrate, ie. M.G. (machine glazed) poster paper. The stencil was made from direct emulsion using a half-tone positive. The print was producer, on an S.P.S. cylinder action screen printing press. The ink was dried through a two lamp S.P.S. U.V. dryer (rated at 300 watt per inch). The resultant dried print was a good half tone image of high definition.

However this initial formulation, when tested, gave poor screen stability. This was improved in a, second embodiment by the addition of n-vinyl pyrrolidone - a solvent miscible with water which also takes part in the curing reaction. A specific formulation of this second embodiment, which likewise had water as the continuous phase and had the resin (amounting to 50% of the emulsion) as the dispersed phase, is given in Example 2.

Example 2 Parts by weight

Laromer* PE 55W⁽¹⁾ 85.3

Darocur* 1173⁽²⁾ 2.0 Aquadisperse* Phthalo Blue GB EP⁽³⁾ 2.7 n-vinyl pyrrolidone (4) 10.0

A composition as formulated in Example 2 was printed and dried in the same manner as for Example 1. The resultant dried print was a good half tone image of high definition.

Due to the relatively high price of this water-miscible solvent, i.e. the n-vinyl pyrrolidone, compared to the other materials used in the formulation, the final material cost was considered uneconomic. To offset this, a calcium carbonate extender was introduced into the composition to obtain a third embodiment with an acceptable raw material cost. A mixture of photoinitiators was also used in place of the single type. A specific formulation of this third embodiment, which likewise had water as the continuous phase and had the resin (amounting to 50% of the emulsion) as the dispersed phase, is given in Example 3.

Example 3 Parts by weight

Emulsion Laromer* PE 55W⁽¹⁾ 63.3

Aquadisperse* Phthalo Blue GB EP^{( 3)} 2.7

N Vinyl Pyrrolidone⁽⁴⁾ 5.0

Omyalite* 95T Extender⁽⁵⁾ 20.0 Photoinitiator Irgacure* 651^{( 6 )} 6.0

Photoinitiator Quantacure* ITX^{( 7)} 3.0 A composition formulated as in Example 3 was printed and dried in the same manner as for Example 1. The resultant dried print was a good half tone image of high definition.

Samples of four colours Trichromatic yellow, magenta, cyan and black were made for container storage stability trials. After four weeks storage, the magenta and black inks had gelled whereas the yellow and cyan were unchanged. Further work was carried out to improve storage stability. In order to retain screen stability and an economic raw materia l cost, a fourth embodiment was devised in which, the n-vinyl pyrrolidone and the photoinitiator mixture were replaced by a solvent, ethoxy-propanol and a single, initiator compound rather than the mixture of photoinitiators. The calcium carbonate extender was also omitted as this was not now required to obtain an acceptable raw material cost. A thickening agent was introduced to maintain the ink at a printable viscosity. Again the emulsion had water as the continuous phase and the resin as the dispersed phase. Slight improvements in screen stability were obtained with this embodiment by the introduction of small amounts of a humectant/surfactant compound and of a silicone emulsion lubricant. A specific formulation of this fourth embodiment is provided in Example 4.

Example 4 Parts by weight

Laromer* PE 55W^{(1 )} 75.2

Darocur* 1173⁽²⁾ 2.9 Ethoxy Propanol⁽⁸⁾ 9.7

Curlout Plus*⁽⁹⁾ 5.8

Alcoprint* PTF⁽¹⁰⁾ 0.5

Alcoprint* PHL⁽¹¹⁾ 1.0

Alcoprint* PSJ⁽¹²⁾ 1.9 Aquadisperse* Phthalo Blue GB EP⁽³⁾ 3.0 A composition formulated as in Example 4 was printed and dried in the same manner as for Example 1. The resultant dried print was a good half tone image of high definition.

The storage stability of trichromatic yellow, magenta, cyan and black printing inks with this latest formulation were then retested and found to be satisfactory.

To provide a completely aqueous-based composition avoiding the use of any inflammable solvents, a fifth embodiment was devised in which the ethoxy propanol was replaced by a mixture of Abater and an acrylic monomer - Tripropylene glycol diacrylate (T.P.G.D.A.) - for maintaining the appropriate dispersion of the resin solids. A specific formulation of this fifth embodiment is provided in Example 5.

Example 5 Parts by weight

Laromer* PE 55W^{(1 )} 61.6

Darocur* 1173⁽²⁾ 3.1

Acrylic Monomer T.P.G.D.A. ^{( 13)} 7.7

Water 15.4

Curlout Plus*⁽⁹⁾ 5.7 Alcoprint* PTF⁽¹⁰⁾ 0.5

Alcoprint* PHL⁽¹¹⁾ 1.0

Alcoprint* PSJ⁽¹²⁾ 2.0

Aquadisperse* Phthalo Blue GB EP⁽³⁾ 3.0

A composition formulated as in Example 5 was printed and dried in the same manner as for Example 1. The resultant dried print was a good half tone image of high definition.

All the above-mentioned tests were carried out using 60" x 40" (1.5m x 1m) machine glazed (M.G.) Poster Paper. It was found that when heavy deposits of colour vere used across the whhle area of the paper, a high degree of curl at the edges of the paper was experienced. This was overcome (in accord with embodiments of the invention of our co-pending UK Patent Applications Nos. 8618595 and 8619245) by providing for the first colour to be printed down onto the paper to be a screen printing ink producing minimal paper curl (e.g. enabling the paper sheet to be re-fed through the printing machine), and for the or each susequent printing thereon to be with a water -based UV curing ink. The screen printing ink producing minimal curl can be a conventional non-aqueous UV curing ink or a conventional solvent-based printing ink, or an aqueous ink of low water content (e.g. less than 20%).

The above-described water-based inks of Examples 1 to 5, when cured only by U.V. radiation, were found to have a wet rub-resistance not adequate for all purposes, and to have a variable gloss level. Experiments were carried out with infra red heating just before the UV curing was effected.

This technique produced prints with good wet rub-resistance and with a substantially uniform level of gloss. It is thought that this was due to the removal of excess water by the infra-red heating. It was also found that more efficient water removal could be achieved by using a jet air dryer to force cold air over the print. It is considered that excess water might be removed, additionally or alternatively, by microwave or radio frequency drying.

Tests were conducted in pasting up the individual sheets to produce hoarding posters, and starch based pastes (obtained from Wilsons Adhesives and Morris Greenhaugh) were used for these tests. The surface of the prints produced by the above ink Examples was found to accept the starch pastes used by bill-posters more readily than prints printed with the solvent-based inks which are currently in general use. Prints produced with the water-based inks of Examples 1 to 5, when dried only by UV radiation, showed excellent adhesion properties with the starch adhesives. These prints when dried both by infra-red and by UV radiation showed a reduction in adhesion properties but this was still an improvement on that attainable with multi-colour prints produced with the standard organic solvent based screen printing inks. Never-theless, by subjecting the prints to corona discharge, this reduction in adhesion properties was overcome and prints with good gloss and wet-rub resistance were still obtained. In a preferred example, prints dried by infra-red and UV radiation were treated to 73 dynes/cm using a Sherman Treaters Corona Discharge Machine. These prints showed the same excellent adhesion properties that were obtained by just drying with UV radiation.

Notes

* means Trade Mark

1. Laromer* PE 55W is a 50% emulsion of a polyester acrylate in water obtainable from B.A.S.F.

2. Darocur* 1173 is a Hydroxy-2-methyl-1-propan-1-one obtainable from E. Merck

3. Aquadisperse* Phthalo Blue GB EP is an aqueous dispersion of pigment Blue 15 obtainable from TennantK.V.K.

4. n-vinyl pyrrolidone is a UV reactive solvent obtainable from B.A.S.F.

5. Omyalite* 95T is a calcium carbonate extender obtainable from Croxton & Garry.

6. Irgacure* 651 is Benzil Dimethyl Ketal obtainable from Ciba Geigy. 7. Quantacure* ITX is isopropylthioxanthon e obtainable from Ward Blenkinsop.

8. Ethoxy Propylenee Glycol Ether obtainable from B.P. Chemicals.

9. Curlout* Plus is a modified acrylic solution polymer obtainable front American Carbonyl Inc.

10. Alcoprint* PTF is an acrylic copolymer in mineral oil thickner obtainable from Allied Colloids.

11. Alcoprint* PHL is a humectant and surfactant blend obtainable from Allied Colloids.

12. Alcoprint* PSJ is a silicone emulsion softner/lubricant obtainable from Allied Colloids.

13. T.P.G.D.A. is a Tripropylene Glycol Diacrylate obtainable from Degussa.

Claims

1. A printing ink for silk screen printing, characterised in that the screen printing ink is a water-based ink that is at least partially curable by irradiation and comprises an emulsion of a resin disposed in water.

2. A screen printing ink according to Claim 1 characterised in that the emulsion has said resin at least substantially in dispersed phase and at least substantially insoluble in the water, the water being the continuous phase of the emulsion.

3. A screen printing ink according to Claim 1 or Claim 2, characterised in that said resin comprises 30% to 60% of the emulsion.

4. A screen printing ink according to any preceding Claim, characterised in that said resin is 50% of the emulsion.

5. A screen printing ink according to any preceding Claim, characterised in that said resin comprises an unsaturated acrylate resin.

6. A screen printing ink according to any preceding Claim, characterised in that said resin comprises a polyester acrylate resin.

7. A screen printing ink according to any preceding Claim, comprising one or more photoinitiators and being at least partially curable by irradiation comprising electromagnetic radiations in the ultra-violet light waveband.

8. A screen printing ink according to any one of Claims 1 to 6, characterised in that said ink is at least partially curable by irradiation with an electron beam.

9. A printing ink according substantially to that of Example 1.

10. A printing ink according substantially to that of Example 2.

11. A printing ink according substantially to that of Example 3.

12. A printing ink according substantially to that of Example 4.

13. A printing ink according substantially to that of Example 5.