WO1990009622A1 - Lithographic printing plate - Google Patents
Lithographic printing plate Download PDFInfo
- Publication number
- WO1990009622A1 WO1990009622A1 PCT/GB1990/000251 GB9000251W WO9009622A1 WO 1990009622 A1 WO1990009622 A1 WO 1990009622A1 GB 9000251 W GB9000251 W GB 9000251W WO 9009622 A1 WO9009622 A1 WO 9009622A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- printing plate
- bottom coating
- plate according
- coating
- substrate
- Prior art date
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/092—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by backside coating or layers, by lubricating-slip layers or means, by oxygen barrier layers or by stripping-release layers or means
Definitions
- This invention relates to a lithographic printing plate and a process for its manufacture.
- the invention has been developed primarily, though not exclusively, in connection with a lithographic printing plate designed to operate with various forms of projection equipment, in which an image is projected onto the plate from a distance.
- Lithographic printing plates of this type are known as "projection speed plates”.
- Projection speed plates are usually prepared by tfie following steps:
- an aluminium substrate is used, and this can include alloys of aluminium of the type suitable for use 'in the production of printing plates.
- tlie substrate is neutralised subsequently by immersion in a strong acid. Removal of further contaminants can also be achieved by this step.
- the surface of the substrate is then modified by a process of "graining". This can be -achieved by a number of techniques, known to those skilled in the a t.
- One method is that of electrical graining, and a variety of acids can be employed, depending on the surface profile required.
- the modified surface is then anodised, to give an aluminium oxide layer which is porous in nature.
- the types of conditions and acids used will determine the final properties of the layer. It can, for example, effect sensitivity, substrate colour, development of the coating, staining, sealing, hardness and durability.
- the anodised layer can be further processed by the application of a variety of materials.
- the purpose of this further treatment is to seal the pores that are formed during the anodisation process.
- silicates are most commonly used; however colloids, inorganic salts, water and steam can be used.
- the present invention has been developed with a view to providing an improved light sensitive coating which reacts much more quickly to the action of low intensity light than is available with existing projection speed plates, and yet which is shielded from what would otherwise be inhibiting effects of the surrounding atmosphere.
- Light sensitive materials used in printing plates are liable to have their response inhibited when exposed to the action of atmospheric oxygen, and this applies particularly to the novel formulation of light sensitive coating provided by the invention, and therefore the invention also requires the provision of a shield or protective top surface layer.
- the invention is therefore concerned with a projection speed plate, and a method of its production, in which a fast response light sensitive coating is applied as a bottom coating to a treated substrate, and an upper coating or top coat is applied which acts as a physical barrier between the bottom coat and atmosphere, so as to prevent or minimise any degradation in the properties of the bottom coating in its response to the application of low intensity 1 ight thereon .
- a lithographic printing plate for use with image projection equipment and comprising a substrate, a light sensitive bottom coating on the substrate, and a top coating on the bottom coating, in which the bottom coating is made of a material having a high sensitivity so as to have a quick response to low intensity light, and yet which is acceptable for use as a printing plate and which is protected from ambient conditions by said top coating.
- the light sensitive bottom coating may be selected from material which has a fast reaction to light images applied thereon by automatic projection equipment, and yet which has satisfactory operating performance under the conditions to which a lithographic plate is normally subjected.
- the bottom coating should retain, during the subsequent treatment of the printing plate, acceptable properties with regard to the following:
- the lower coating or bottom coat is in contact with the substrate and is light sensitive, whereas the upper coating or top coat acts as a physical barrier between the bottom coat and atmosphere.
- the bottom coat may be applied as a coating which comprises the following general types of materials:
- resins which can be (a) monomers which are normally multi-functional acrylates or methacr lates in ranges 5 to 50%; (b) prepolymers which can be a variety of different types of acrylics of medium molecular weight, such as polyester acrylates, urethane acrylates, epoxy acrylates and methacrylates and co-polymers of acrylates and methacrylates in the range 5 to 70%.
- Monomers and prepolymers polymerise upon exposure to light when in conjunction with an appropriate sensitiser/initiator. Slight polymerisation only can be achieved without sensitisers/ initiators.
- Polyester acr-ylate is a particularly preferred resin for use in the bottom coating, as it is U.V. curable and highly reactive, so as to give a fast cure speed.
- a preferred sensitiser / initiator for use with polyester acrylate is triazine (thio-phenyl-triazine) , though other sensitiser / initiators may be used, such as thioxanthone.
- thioxanthone used in a dicarboxyic acid derivative of thioxanthone.
- Binders may also be used in conjunction with the resins, and may be vinyl resins and especially a polyvinyl butyral vinyl resin, cellulosic resins, esters, ethers and solid acrylics with low reactivity, all within the range 5 to 50%.
- Polyvinyl butyral is particularly useful in its function as a binder, because it imparts good adhesion and abrasion-resistant properties.
- Plasticisers may also be used, including phthalates, glycols esters and vinyl compounds, all within the range 1 to 50%.
- sensitisers may include any of the following: a) thioxanthones (referred to above) b) triazines (referred to above) c) titanocenes d) coumarins e) amines f) fluorescent dyes g) mixture of the above
- colour change components such as pH dyes, leuco dyes, and photochromies.
- adhesion promoters such as silanes.
- Items (iii) to (viii) may each be incorporated in the range 0.1 to 10%.
- the top coat may comprise any one of the following, by way of example:
- Polyvinyl alcohols have been found to be particularly suitable for the top coating in order to protect the sensitive bottom coating. '
- wetting agent some small amount will be desirable usually about 0.'2% and upwards of this amount to about 50%. Any material which has suitable wetting characteristics may be used. Colouring dyes, pigments and/or colour change components may additionally be added in a range 0.1 to 20% into the top coat/wetting agent mixture.
- Bottom coat preferably 1.0 gramms per square metre (range 0.25 - 3.0 gramms per square metre)
- Top coat preferably 1.0 gramms per square metre (range 0.25 - 3.0 gramms per square metre)
- the invention is further concerned with a method of preparing a lithographic printing plate as defined according to said one aspect of the- invention, and/or with any of the preferred formulations referred to herein.
- One preferred formulation contains the following components:
- Item (c) shows use of a polyhydroxy ether as a binder.
- a vinyl resin may be used, and particularly polyvinyl butyral.
- a small undefined quantity of a surfactant may be added to improve cosmetics.
- Resin (a) 83.4% polyvinyl alcohol (TM G0HSEN0L KH17 ex Nippon Gohsei ) .
- Vetting Agent (b) 16.6% modified alcohol ethoxylate (TM ethylan CPG660 ex HARCOS).
- This top coat was applied by the use of"Water as a solvent, while the bottom coat is normally applied with the use of an organic solvent, such as a variety of glycols.
- polyvinyl alcohol in the top coat protects the sensitive bottom coating, by acting as a barrier to the transfer of oxygen from the atmosphere to the bottom coating.
- oxygen radicals would interfere with free radical polymerisation, by having a quenching effect, and would therefore severely reduce the cure speed of the bottom coating.
- photoinitiation in the bottom coating is more effective, and therefore the cure speed is greatly improved.
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- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
There is disclosed a lithographic printing plate for use with image projection equipment and which comprises a substrate, a light sensitive bottom coating on the substrate, and a protective top coating on the bottom coating, in which the bottom coating is made of a material having a high sensitivity so as to have a quick response to low intensity light, and yet which is acceptable for use as a printing plate and which is protected from ambient conditions by the top coating. The preferred material from which the bottom coating is made comprises a polyester acrylate resin, and the preferred material for the top coating is a polyvinyl alcohol.
Description
LITHOGRAPHIC PRINTING PLATE
This invention relates to a lithographic printing plate and a process for its manufacture.
The invention has been developed primarily, though not exclusively, in connection with a lithographic printing plate designed to operate with various forms of projection equipment, in which an image is projected onto the plate from a distance. Lithographic printing plates of this type are known as "projection speed plates".
The problems normally associated with a projection speed plate are:
1. That the intensity of light of the projected image is low, and therefore high light sensitivity is required from the coating applied to the printing plate; and,
2. High reproduction is difficult to achieve. Projection speed plates are usually prepared by tfie following steps:
1. Substrate
(a) an aluminium substrate is used, and this can include alloys of aluminium of the type suitable for use 'in the production of printing plates.
(b) the substrate undergoes a number of processes which prepare it to receive a light sensitive layer, theεϊe
* f • -ha processes including the following steps:
(i) cleaning the substrate to remove milling oil* a d" other surface material. This can be achieved by a variety of chemical treatments, but the most common of whic"h is έ.n alkali cleaning treatment.
(ii) if an alkali is used as just referred to, tlie substrate is neutralised subsequently by immersion in a strong acid. Removal of further contaminants can also be achieved by this step.
(iii) the surface of the substrate is then modified by a process of "graining". This can be -achieved by a number of techniques, known to those skilled in the a t.
One method is that of electrical graining, and a variety of acids can be employed, depending on the surface profile required.
(iv) the modified surface is then anodised, to give an aluminium oxide layer which is porous in nature. The types of conditions and acids used will determine the final properties of the layer. It can, for example, effect sensitivity, substrate colour, development of the coating, staining, sealing, hardness and durability.
(v) if required, the anodised layer can be further processed by the application of a variety of materials. The purpose of this further treatment is to seal the pores that are formed during the anodisation process. Typically, silicates are most commonly used; however colloids, inorganic salts, water and steam can be used.
(vi) following this stage, suitable light sensitive coatings can be applied.
Given that the intensity of light of a projected image on a projection speed plate is low, high light sensitivity is required from the coating system, and the present invention has been developed with a view to providing an improved light sensitive coating which reacts much more quickly to the action of low intensity light than is available with existing projection speed plates, and yet which is shielded from what would otherwise be inhibiting effects of the surrounding atmosphere.
Light sensitive materials used in printing plates are liable to have their response inhibited when exposed to the action of atmospheric oxygen, and this applies particularly to the novel formulation of light sensitive coating provided by the invention, and therefore the invention also requires the provision of a shield or protective top surface layer.
The invention is therefore concerned with a projection speed plate, and a method of its production, in which a fast response light sensitive coating is applied as a
bottom coating to a treated substrate, and an upper coating or top coat is applied which acts as a physical barrier between the bottom coat and atmosphere, so as to prevent or minimise any degradation in the properties of the bottom coating in its response to the application of low intensity 1 ight thereon .
According to one aspect of the invention there is provided a lithographic printing plate for use with image projection equipment and comprising a substrate, a light sensitive bottom coating on the substrate, and a top coating on the bottom coating, in which the bottom coating is made of a material having a high sensitivity so as to have a quick response to low intensity light, and yet which is acceptable for use as a printing plate and which is protected from ambient conditions by said top coating.
Thus, the light sensitive bottom coating may be selected from material which has a fast reaction to light images applied thereon by automatic projection equipment, and yet which has satisfactory operating performance under the conditions to which a lithographic plate is normally subjected. In particular, the bottom coating should retain, during the subsequent treatment of the printing plate, acceptable properties with regard to the following:
(a) plate colour
(b) durability on a press run
(c) solvent resistance
(d) image colour retention
(e) colour change properties
(f) shelf life
(g) development
With existing speed projection plates, all of these properties are liable to be sacrificed to some extent in the formulation of light sensitive coatings having quick response to light.
Thus, in a printing plate according to the invention, the lower coating or bottom coat is in contact with the
substrate and is light sensitive, whereas the upper coating or top coat acts as a physical barrier between the bottom coat and atmosphere.
The bottom coat may be applied as a coating which comprises the following general types of materials:
(i) resins, which can be (a) monomers which are normally multi-functional acrylates or methacr lates in ranges 5 to 50%; (b) prepolymers which can be a variety of different types of acrylics of medium molecular weight, such as polyester acrylates, urethane acrylates, epoxy acrylates and methacrylates and co-polymers of acrylates and methacrylates in the range 5 to 70%.
Monomers and prepolymers polymerise upon exposure to light when in conjunction with an appropriate sensitiser/initiator. Slight polymerisation only can be achieved without sensitisers/ initiators.
Polyester acr-ylate is a particularly preferred resin for use in the bottom coating, as it is U.V. curable and highly reactive, so as to give a fast cure speed.
A preferred sensitiser / initiator for use with polyester acrylate is triazine (thio-phenyl-triazine) , though other sensitiser / initiators may be used, such as thioxanthone. A preferred form of thioxanthone used in a dicarboxyic acid derivative of thioxanthone.
Binders may also be used in conjunction with the resins, and may be vinyl resins and especially a polyvinyl butyral vinyl resin, cellulosic resins, esters, ethers and solid acrylics with low reactivity, all within the range 5 to 50%. Polyvinyl butyral is particularly useful in its function as a binder, because it imparts good adhesion and abrasion-resistant properties.
Plasticisers may also be used, including phthalates, glycols esters and vinyl compounds, all within the range 1 to 50%.
(ii) sensitisers / initiators / activators. The sensitisers may include any of the following:
a) thioxanthones (referred to above) b) triazines (referred to above) c) titanocenes d) coumarins e) amines f) fluorescent dyes g) mixture of the above
These can be incorporated within the range 1 to 30%.
(iii) colour change components, such as pH dyes, leuco dyes, and photochromies.
(iv) colouring dyes and pigments.
(v) oxygen scavengers, such as amines.
(vi) adhesion promoters, such as silanes.
(vii) stabilisers, such as quinone based materials.
(viii) wetting agents.
Items (iii) to (viii) may each be incorporated in the range 0.1 to 10%.
The percentages of the above components can vary widely, depending on the formulation employed. All percentages quoted are by weight.
The top coat may comprise any one of the following, by way of example:
(a) acrylics
(b) N-vinyl pyrolidone
(c) carboxy methyl cellulose ' *
(d) gums
(e) shellac
(f) polyvinyl alcohols
All of these may come within the range 50 to 99%.
Polyvinyl alcohols have been found to be particularly suitable for the top coating in order to protect the sensitive bottom coating. '
In all of the above examples, some small amount of wetting agent will be desirable usually about 0.'2% and upwards of this amount to about 50%. Any material which has suitable wetting characteristics may be used.
Colouring dyes, pigments and/or colour change components may additionally be added in a range 0.1 to 20% into the top coat/wetting agent mixture.
Bottom coat preferably 1.0 gramms per square metre (range 0.25 - 3.0 gramms per square metre)
Top coat preferably 1.0 gramms per square metre (range 0.25 - 3.0 gramms per square metre)
The invention is further concerned with a method of preparing a lithographic printing plate as defined according to said one aspect of the- invention, and/or with any of the preferred formulations referred to herein.
One preferred formulation contains the following components:
1. Resins
(a) 23.2% dipentaerythritol monohydroxypenta acrylate. (Available under TM sartomer SR399)
Structure
(b) 32.7% polyester acrylate (straight) (TM Ebecryl 810 ex UCB chemicals)
(c) 37.4% phenol, 4, 4' - ( 1-methylethylidene) bis-polymer with (chloromethyl ) oxirane (formulae
C15H16°2-C3H5CL0)x
Molecular weight more than 30,000
(TM Phenoxy PKHH ex Union Carbide)
(d) Initiator/sensitiser
(e) 2.8% Thioxanthone of unknown structure (which may be as disclosed in more detail in US patent 4585876 or 4385182). Preferably,
f) 1.9% 4 methyl thiophenyl triazine
Chemical formula subject of British patent application No 8627059.
(g) 1.9% orasol pink (solvent red 127) ex Ciba Geigy.
Item (c) shows use of a polyhydroxy ether as a binder. As an alternative binder material, a vinyl resin may be used, and particularly polyvinyl butyral.
In addition to the above components, a small undefined quantity of a surfactant may be added to improve cosmetics.
Top Coat
Resin (a) 83.4% polyvinyl alcohol (TM G0HSEN0L KH17 ex Nippon Gohsei ) .
Vetting Agent (b) 16.6% modified alcohol ethoxylate (TM ethylan CPG660 ex HARCOS).
This top coat was applied by the use of"Water as a solvent, while the bottom coat is normally applied with the use of an organic solvent, such as a variety of glycols.
The use of polyvinyl alcohol in the top coat protects the sensitive bottom coating, by acting as a barrier to the transfer of oxygen from the atmosphere to the bottom coating. In the absence of this barrier layer, oxygen radicals would interfere with free radical polymerisation, by having a quenching effect, and would therefore severely reduce the cure speed of the bottom coating. By eliminating oxygen, photoinitiation in the bottom coating is more effective, and therefore the cure speed is greatly improved.
Example 1
Developer - commercial name new Aquarius Hand Developer from Horsell.
Formulations used and results '
Bottom coat 1 gramms per square metre Top coat 1 gramms per square metre Developer new Aquarius Hand Developer for 1 min at 20°C Bottom coat formulation
32.4% ebecryl 810 (U.V. curable acrylic) 23.1% sartomer SR399 37% phenoxy PKHH 2.7% RT956 (thioxanthone) 1.8% 4 methyl thio phenyl triazine 1% leuco crystal violet 1% waxoline blue (dyestuff) 1% FC431 (surfactant from 3M) Top coat as per preferred formulation stated earlier Exposed on a projection system commercially available from Rachwal
Exposure time 6 seconds 1050 - 1100 watt bulb Result obtained was good
Developed with new Aquarius Hand Developer 1 min at 20°C Exposed on a. conventional light frame 4 watts Exposure time 0.8 seconds
Developed with new Aquarius Hand Developer for 1 min at 20°C On a continuous Stouffer sensitivity wedge, a result of S5-C11 was obtained.
Comparative test with an Aquarius plate (commercially available from Horsell)
Under the same conditions exposed for 66 seconds and gave a result of S4-C10 on the Stouffer wedge.
The conclusion reached from the comparative example is that a substantially more sensitive plate (negative) has been obtained, which is particularly suitable for use as a projection speed plate where low intensity light is used to project an image onto the plate. If required, dye stuffs
may be incorporated as a separate layer on the substrate.
Claims
1. A lithographic printing plate for use with image projection equipment and comprising a substrate, a light sensitive bottom coating on the substrate, and a top coating on the bottom coating, in which the bottom coating is made of a material having a high sensitivity so as to have a quick response to low intensity light, and yet which is acceptable for use as a printing plate and which is protected from ambient conditions by said top coating.
2. A printing plate according to Claim 1, in which the bottom coating comprises monomer or pre-polymer resin.
3. A printing plate according to Claim 2, in which the bottom coating comprises a polyester acrylate resin.
4. A printing plate according to Claim 3, in which the bottom coating includes a sensitiser / initiator of triazine.
5. A printing plate according to Claim 3 or 4, in which the bottom coating includes a binder.
6. A printing plate according to "Claim 5, in which the binder comprises polyvinyl butyral.
7. A printing plate according to Claim 3, in which the bottom coating includes a sensitiser / initiator of thioxanthone.
8. A printing plate according to Claim 7, in which the sensitiser / initiator is a thioxanthone dicarboxylic acid derivative.
9. A printing plate according to any one of the preceding claims, in which the top coating comprises a polyvinyl alcohol.
10. A printing plate according to any one of the preceding claims, and including dye stuff as a separate layer.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8903691.7 | 1989-02-17 | ||
| GB898903691A GB8903691D0 (en) | 1989-02-17 | 1989-02-17 | Lithographic printing plate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1990009622A1 true WO1990009622A1 (en) | 1990-08-23 |
Family
ID=10651897
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/GB1990/000251 WO1990009622A1 (en) | 1989-02-17 | 1990-02-15 | Lithographic printing plate |
Country Status (2)
| Country | Link |
|---|---|
| GB (1) | GB8903691D0 (en) |
| WO (1) | WO1990009622A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2288032A (en) * | 1994-03-12 | 1995-10-04 | Horsell Plc | Photolithographic printing plate |
| US5609993A (en) * | 1991-04-17 | 1997-03-11 | Nippon Paint Co., Ltd. | Process for producing lithographic printing plate, photosensitive plate and aqueous ink composition therefor |
| US5786127A (en) * | 1996-08-15 | 1998-07-28 | Western Litho Plate & Supply Co. | Photosensitive element having an overcoat which increases photo-speed and is substantially impermeable to oxygen |
| EP1081552A1 (en) * | 1999-09-03 | 2001-03-07 | Fuji Photo Film Co., Ltd. | Lithographic printing plate precursor |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0275147A2 (en) * | 1987-01-12 | 1988-07-20 | E.I. du Pont de Nemours and Company | Improvements in or relating to printing plate precursors |
-
1989
- 1989-02-17 GB GB898903691A patent/GB8903691D0/en active Pending
-
1990
- 1990-02-15 WO PCT/GB1990/000251 patent/WO1990009622A1/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0275147A2 (en) * | 1987-01-12 | 1988-07-20 | E.I. du Pont de Nemours and Company | Improvements in or relating to printing plate precursors |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5609993A (en) * | 1991-04-17 | 1997-03-11 | Nippon Paint Co., Ltd. | Process for producing lithographic printing plate, photosensitive plate and aqueous ink composition therefor |
| GB2288032A (en) * | 1994-03-12 | 1995-10-04 | Horsell Plc | Photolithographic printing plate |
| US5786127A (en) * | 1996-08-15 | 1998-07-28 | Western Litho Plate & Supply Co. | Photosensitive element having an overcoat which increases photo-speed and is substantially impermeable to oxygen |
| EP1081552A1 (en) * | 1999-09-03 | 2001-03-07 | Fuji Photo Film Co., Ltd. | Lithographic printing plate precursor |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8903691D0 (en) | 1989-04-05 |
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