CA1164267A - Dry planographic printing plate and preparation thereof - Google Patents
Dry planographic printing plate and preparation thereofInfo
- Publication number
- CA1164267A CA1164267A CA000365953A CA365953A CA1164267A CA 1164267 A CA1164267 A CA 1164267A CA 000365953 A CA000365953 A CA 000365953A CA 365953 A CA365953 A CA 365953A CA 1164267 A CA1164267 A CA 1164267A
- Authority
- CA
- Canada
- Prior art keywords
- plate
- photosensitive layer
- silicone rubber
- developer
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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
- G03F7/075—Silicon-containing compounds
- G03F7/0752—Silicon-containing compounds in non photosensitive layers or as additives, e.g. for dry lithography
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A presensitized planographic printing master plate is provided herein requiring no dampening water for use in negative work.
The plate comprises a base substrate, a light releasing photosensitive layer overlying the base substrate and a silicone rubber layer overlying the photosensitive layer. When the printing master plate is exposed through a negative film and then is treated with a developer, only the silicone rubber layer overlying the exposed photosensitive layer is removed, while the photosensitive layer remains as it is to form an image area. Dampening water is not required when printing is carried out.
A presensitized planographic printing master plate is provided herein requiring no dampening water for use in negative work.
The plate comprises a base substrate, a light releasing photosensitive layer overlying the base substrate and a silicone rubber layer overlying the photosensitive layer. When the printing master plate is exposed through a negative film and then is treated with a developer, only the silicone rubber layer overlying the exposed photosensitive layer is removed, while the photosensitive layer remains as it is to form an image area. Dampening water is not required when printing is carried out.
Description
llS~2~
This invention relates to a dry planographic prin-ting plate and a method of making same. More particularly, it is concerned ~ith a new type of a negative working presensitized planographic printing plate for use in dry planography, and with a method making same.
Heretofore, several proposals have been made concerning a nega-tive working dry planographic printing plate comprising a silicone rubber layer which overlies a photosensitive layer overlying a base substrate.
For example, in Japanese Patent Publication No. 16044/1971 a presensitized planographic printing plate is proposed comprisiny a silicone rubber layer adhered by an adhesive layer to a light solubilizable dia-zonium type photosensitive layer overlying an aluminum plate. The plate is exposed to actinic light through a negative film to solubilize the photosensitive layer of the exposed area. Then a developer is used to dissolve of the solubilized photosensitive ]ayer and at the same time the overlying silicone rubber layer is removed to allow the aluminum plate as a base substrate to be exposed as an image area.
Also in Japanese Patent Laid Open Publications Nos. 8306/1974 and 73202/1974 and Japanese Patent Application No. 131797/1978, a negative working dry planographic printing plate is proposed having the same con-struction as above described wherein the solubilized photosensitive layer and the overlying silicone rubber layer are removed by development and the exposed portion of the base substrate constitutes an image area.
In those proposed printing plates, the image area has a similar structure to that of a deep etched plate wherein the ink receiving portion consists of recesses (hereinafter referred to as "cell(s)") formed by the removal of the solubilized photosensitive layer and the overlying silicone rubber layer. In such a printing plate, it has heretofore been necessary to feed a larger amount of ink onto the printing plate in order to allow .
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ink to adhere sufficiently to the cell portion at the tiine of printiny This, however, results in a large increase in the volume of ink. consumption, leading not only to an inCrQase in the printing cost but also to a serious problem in point of printing effect, namely in the reproduction of grada-tion. For example, in the case of feeding ink onto a printing plate so as to give a desirable optical density of the so-called solid portion of the resulting printed matter, the ink is not sufficiently transferred from the form roller of a printing machine into the cells on the plate forming a dot image of the so-called highlight portion of the printed matter, particularly into the cells forming very small dots. Thus~ the dots of the printed ~atter tend to get out of shape, or sometimes dot omission occurs in the printed matter due to there being no transfer of ink into the cells.
On the other hand, if the amount of ink to be fed onto the plate surface is increased in order to attempt to eliminate such disorder of dot shape, the optical density of the solid portion becomes too high with loss in printing effect balance; sometimes there may occur a serious problem associated with the print quality, for examplel the dots in the shadow area are not ~eproduced.
To solve these problems, it may be effective to reduce the film thickness of the photosensitive layer to be dissolved off and thereby to make the cell depth smaller. However, it is very difficult and not practi-cal uniformly to form a photosensitive layer having a thickness required to solve the foregoing problems associated with printing, e.g. a film thickness of 0.1 p. Further, thinning the photosensitive layer results in an en-hanced physical and chemical influence from the base substrate, for example, the image reproducibility and the preservability are badly influenced in .- ~
~ many cases.
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Thus, the negative worklng dry planographic printiny plates so far proposed have drawbacks in point of ink adhesion, etc. and are less practlcal .
It is an objec~ of one aspect of this invention to minimi7e and even to tend to eliminate the above-mentioned disadvantages.
It is an object of another aspect of this invention to provide a new negative working dry planographic printing plate and a method of making the same.
~ ccording to one aspect of this invention, a negative working pre-sensitized printing plate is provided for use in dry planography, which plate comprises (l~ a base substrate, (2) an oleophilic photosensitive layer secured to, and overlying, the base substrate, and (3) an ink-repelling silicone rubber layer secured to, and overlying, the photosensitive layer, the photosensitive layer being substantially insoluble in a developer both before and after the exposure to the actinic light, and being capable of re-leasing the silicone rubber layer in a selected area to be exposed to the actinic light, and the silicone rubber layer being capable of being removed in the exposed image area by a developer.
By another aspect of this invention, a negative working presensi-tized planographic printing plate is provided for use in dry planography, comprising an image area constituted by a photosensitive layer overlying a base substratej and an non~image area constituted by a silicone rubber layer overlying the photosensitive layer.
By a variant thereof, the photosensitive layer is made difficult to dissolve or insoluble in the developer by cross-linking a quinonediazide compound with a polyfunctional compound.
By one variation thereof, the quinonediazide compound is naphthoquinone-1,2-diazide su1fonate with a polyhydroxy compound.
,~ - 3 -., ..- ~
.
By another varia~ion thereo, the q~inonediazide compo~nd is naphthoquincne-1,2-diazide sulfonate with a phenol-formaldehyde novolak resin.
By another variant, the photosensitive layer is made difficult to dissolve or insoluble in the developer by cross-linking a quinonediazide compound with a polyisocyanate compound.
By yet another variant, the photosensitive layer is made diffi-cult to dissolve or insoluble in the developer by cross-linking a quinone-diazide compound with a polyepo~y compound.
By another variant, the photosensitive layer is made difficult to dissolve or insoluble in the developer by urethanizing a quinonediazide compound with a monoisocyanate.
By yet another variant, the photosensitive layer is made difficult to dissolve or insoluble in the developer by esterifying a quinonediazide compound.
By still another variant, the photosensitive layer is made difiicult to dissolve or insoluble in the developer by amidizing a quinonediazide compound.
By yet a further variant, the photosensitive layer is made diffi-cult to dissolve or insoluble in the developer by graft polymerizing aquinonediazide compound with a vinyl monomer.
By a still further variant, the thickness of the photosensitive layer is in the range of from O.l to lO0 ~.
By another variant, the silicone rubber layer comprises a cross-linked diorganopolysiloxane obtained by curing diorganopolysiloxane having the followlng repeating unit:
_ 4 ;
, j. , , ~ ~6~6~
R
l . ', ---- si--~ _ R ~ n wherein n is an integer not less than 1 and R, which may be alike or di~ferent, is each Cl to C10 alkyl, alkenyl or phenyl with 60% or more of R being a methyl group.
By a variation thereof, the thickness of the silicone rubber layer is in the range of from 0.5 to 10 ~.
By yet another aspect of this invention, a methad is provided for making a negative working presensitized planographic printing plate for use in dry planography, which method comprises: image-wise exposing a printing master, the printing master comprising a base substrate, a photo-sensitive layer being difficult to dissolve or insoluble in a developer and overlying the base substrate, and a silicone rubber layer overlying the photosensltive Iayer; and subsequently treating the exposed printing master with the developer to allow only the exposed image areas of the silicone rubber layer to be removed.
The photosensitlve layer used in aspects of this invention is difflcult to dissolve or lnsoluble in a developer, that is, it is a light releasing layer, which on developing allows only the overlying silicone rubber layer to be removed, leaving the exposed portion o~ the photosensi-tive layer as lt is without substantial removal thereof.
Such a light releasing layer is obtained by rendering a known ; light-solubillzable phctosensitive compound difficult to dissolve or in-soluble in a developer by cross-linking that compound with a polyfunctional compound or by modifying a functional group contained in that compound with - 4a~
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:. ~
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.
This invention relates to a dry planographic prin-ting plate and a method of making same. More particularly, it is concerned ~ith a new type of a negative working presensitized planographic printing plate for use in dry planography, and with a method making same.
Heretofore, several proposals have been made concerning a nega-tive working dry planographic printing plate comprising a silicone rubber layer which overlies a photosensitive layer overlying a base substrate.
For example, in Japanese Patent Publication No. 16044/1971 a presensitized planographic printing plate is proposed comprisiny a silicone rubber layer adhered by an adhesive layer to a light solubilizable dia-zonium type photosensitive layer overlying an aluminum plate. The plate is exposed to actinic light through a negative film to solubilize the photosensitive layer of the exposed area. Then a developer is used to dissolve of the solubilized photosensitive ]ayer and at the same time the overlying silicone rubber layer is removed to allow the aluminum plate as a base substrate to be exposed as an image area.
Also in Japanese Patent Laid Open Publications Nos. 8306/1974 and 73202/1974 and Japanese Patent Application No. 131797/1978, a negative working dry planographic printing plate is proposed having the same con-struction as above described wherein the solubilized photosensitive layer and the overlying silicone rubber layer are removed by development and the exposed portion of the base substrate constitutes an image area.
In those proposed printing plates, the image area has a similar structure to that of a deep etched plate wherein the ink receiving portion consists of recesses (hereinafter referred to as "cell(s)") formed by the removal of the solubilized photosensitive layer and the overlying silicone rubber layer. In such a printing plate, it has heretofore been necessary to feed a larger amount of ink onto the printing plate in order to allow .
B
~. . . . . .
.
.
.
. . .
.. ...
.
ink to adhere sufficiently to the cell portion at the tiine of printiny This, however, results in a large increase in the volume of ink. consumption, leading not only to an inCrQase in the printing cost but also to a serious problem in point of printing effect, namely in the reproduction of grada-tion. For example, in the case of feeding ink onto a printing plate so as to give a desirable optical density of the so-called solid portion of the resulting printed matter, the ink is not sufficiently transferred from the form roller of a printing machine into the cells on the plate forming a dot image of the so-called highlight portion of the printed matter, particularly into the cells forming very small dots. Thus~ the dots of the printed ~atter tend to get out of shape, or sometimes dot omission occurs in the printed matter due to there being no transfer of ink into the cells.
On the other hand, if the amount of ink to be fed onto the plate surface is increased in order to attempt to eliminate such disorder of dot shape, the optical density of the solid portion becomes too high with loss in printing effect balance; sometimes there may occur a serious problem associated with the print quality, for examplel the dots in the shadow area are not ~eproduced.
To solve these problems, it may be effective to reduce the film thickness of the photosensitive layer to be dissolved off and thereby to make the cell depth smaller. However, it is very difficult and not practi-cal uniformly to form a photosensitive layer having a thickness required to solve the foregoing problems associated with printing, e.g. a film thickness of 0.1 p. Further, thinning the photosensitive layer results in an en-hanced physical and chemical influence from the base substrate, for example, the image reproducibility and the preservability are badly influenced in .- ~
~ many cases.
, . ':
~ 164.~
Thus, the negative worklng dry planographic printiny plates so far proposed have drawbacks in point of ink adhesion, etc. and are less practlcal .
It is an objec~ of one aspect of this invention to minimi7e and even to tend to eliminate the above-mentioned disadvantages.
It is an object of another aspect of this invention to provide a new negative working dry planographic printing plate and a method of making the same.
~ ccording to one aspect of this invention, a negative working pre-sensitized printing plate is provided for use in dry planography, which plate comprises (l~ a base substrate, (2) an oleophilic photosensitive layer secured to, and overlying, the base substrate, and (3) an ink-repelling silicone rubber layer secured to, and overlying, the photosensitive layer, the photosensitive layer being substantially insoluble in a developer both before and after the exposure to the actinic light, and being capable of re-leasing the silicone rubber layer in a selected area to be exposed to the actinic light, and the silicone rubber layer being capable of being removed in the exposed image area by a developer.
By another aspect of this invention, a negative working presensi-tized planographic printing plate is provided for use in dry planography, comprising an image area constituted by a photosensitive layer overlying a base substratej and an non~image area constituted by a silicone rubber layer overlying the photosensitive layer.
By a variant thereof, the photosensitive layer is made difficult to dissolve or insoluble in the developer by cross-linking a quinonediazide compound with a polyfunctional compound.
By one variation thereof, the quinonediazide compound is naphthoquinone-1,2-diazide su1fonate with a polyhydroxy compound.
,~ - 3 -., ..- ~
.
By another varia~ion thereo, the q~inonediazide compo~nd is naphthoquincne-1,2-diazide sulfonate with a phenol-formaldehyde novolak resin.
By another variant, the photosensitive layer is made difficult to dissolve or insoluble in the developer by cross-linking a quinonediazide compound with a polyisocyanate compound.
By yet another variant, the photosensitive layer is made diffi-cult to dissolve or insoluble in the developer by cross-linking a quinone-diazide compound with a polyepo~y compound.
By another variant, the photosensitive layer is made difficult to dissolve or insoluble in the developer by urethanizing a quinonediazide compound with a monoisocyanate.
By yet another variant, the photosensitive layer is made difficult to dissolve or insoluble in the developer by esterifying a quinonediazide compound.
By still another variant, the photosensitive layer is made difiicult to dissolve or insoluble in the developer by amidizing a quinonediazide compound.
By yet a further variant, the photosensitive layer is made diffi-cult to dissolve or insoluble in the developer by graft polymerizing aquinonediazide compound with a vinyl monomer.
By a still further variant, the thickness of the photosensitive layer is in the range of from O.l to lO0 ~.
By another variant, the silicone rubber layer comprises a cross-linked diorganopolysiloxane obtained by curing diorganopolysiloxane having the followlng repeating unit:
_ 4 ;
, j. , , ~ ~6~6~
R
l . ', ---- si--~ _ R ~ n wherein n is an integer not less than 1 and R, which may be alike or di~ferent, is each Cl to C10 alkyl, alkenyl or phenyl with 60% or more of R being a methyl group.
By a variation thereof, the thickness of the silicone rubber layer is in the range of from 0.5 to 10 ~.
By yet another aspect of this invention, a methad is provided for making a negative working presensitized planographic printing plate for use in dry planography, which method comprises: image-wise exposing a printing master, the printing master comprising a base substrate, a photo-sensitive layer being difficult to dissolve or insoluble in a developer and overlying the base substrate, and a silicone rubber layer overlying the photosensltive Iayer; and subsequently treating the exposed printing master with the developer to allow only the exposed image areas of the silicone rubber layer to be removed.
The photosensitlve layer used in aspects of this invention is difflcult to dissolve or lnsoluble in a developer, that is, it is a light releasing layer, which on developing allows only the overlying silicone rubber layer to be removed, leaving the exposed portion o~ the photosensi-tive layer as lt is without substantial removal thereof.
Such a light releasing layer is obtained by rendering a known ; light-solubillzable phctosensitive compound difficult to dissolve or in-soluble in a developer by cross-linking that compound with a polyfunctional compound or by modifying a functional group contained in that compound with - 4a~
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.
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a monofunctional cornpound. By way of illustrating such lLght-solubiLizable photosensitive compound, mention may be rnade of quinonediazides usually employed for positive working presensitized plate, wipe-on plate or photo-resist, e.g., benzoquinone-1,2-diazide sulfonates or naphthoquinone-1,2-diazide sulfonates with polyhydoxy compounds, e.g., the ester from benzo-quinone-1,2-diazide sulfochloride and polyhydroxyphenyl~ the ester from naphthoquinone-1,2-diazide sulfochloride and pyrogallol acetone resin, or the ester from naphthoquinone-1,2-diazide sulfochloride and phenol-formaldehyde novolak resin, or complexes of diazonium compounds and inorganic or organic acids, e.g., a photosensitive complex of diazodi-phenylamine and phosphotungstic acid.
., .
- 4b -`:' ' An example of the rne~hod of introducing a cross-linked str~cture into such a light-solubilizable photosensitive compotmd, includes a method wherein reactive groups, e.g. hydroxyl and amino, contained in the said photosensitive compound are cross-linked with a polyfunctional cross-linking agent.
Examples of such cross-linking agents are poly:isocyanate compounds, e.g. paraphenylene diisocyanate, 2,~- or 2,6-toluene dlisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, or adducts thereof, and polyepoxy compounds, e.g. polyethylene glycol diglycidyl ethers, polypropylene glycol diglycidyl ethers, bisphenol A diglycidyl ether, and trimethyl-olpropane triglycidyl ether. It is necessary that the curing operation with these cross-linking agents be carried out under conditions under which the photosensitive substance will not lose its photosensitivity, usually at a temperature not higher than ~20C. To this end, a catalyst or the like is used.
Another method of rendering such light-solubilizable photosensitive compound difficult to dissolve or insoluble in a developer involves, for example, urethanizing, esterlfying or amidizing a functional group contained in the photosensitive compound. The compound to be reacted with such functional group of the photosensitive compound may be either a low molecular or relatively high molecular compound. Alternatively, a vinyl monomer may be graft-polymerized to the photosensitive compound.
A specially preferred photosensitive layer used in aspects of this invention is obtained by cross-linking or modifying a partial ester from naphthoquinone-1~2-diazide-5-sulfochloride and phenol-formaldehyde novolak resin with a poly- or mono-functional isocyanate.
Other components may be incorporated on the photosensitive layer with a view to improYing tlle film-forming property or the adhesion to the base substrate, or dyest~l~s for making image vislble _ 5 _ ` .
:
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at the time of development or exposure, provid~d that such incorporation should not spoil the effect of aspects of this invention.
The thickness of the li~ht-releasing layer used in aspects of this invention is in the ranye of 0.1 to 100 ~u, preferably from 0.5 to 10 ~. A smaller thickness is likely to cause defects, e.g. the formation of pinholes at the time of coating, while a larger thickness is disadvantageous from the economic point of view.
The silicone rubber layer used in aspects of this invention consists maily of a linear organopolysiloxane of several thousand to several hundred thousand molecular weights having the following repeating unit:
~ R
Or R n wherein n is an integer not less than 1 and R i8 Cl to C10 alkyl, alkenyl or phenyl with 60% or more of R being preferably methyl gro~p_ Such a linear organopDlysiloxane may be mixed with an organic peroxide and heat-treated to give a scarcely cross-linked silicone rubber.
Also added to the linear organopolyslloxane is a cross-linking agent which is the so-called room temperature (low temperature) vulcanizing type used for silicone rubber, e.g. acetoxysilanes, ketoximosilanes, alkoxysilanes, aminosilanes and amidesilanes. Using these cross-linking agents in combination with a hydroxyl-terminated linear organopolysiloxane respectively a~ford deacetic-acid type, deoxime type, dealcohol-type, deamine type and deamide_type silicone rubbers. To these sillcone rubbers, in general, is further added a small amount of an organotin compound or
a monofunctional cornpound. By way of illustrating such lLght-solubiLizable photosensitive compound, mention may be rnade of quinonediazides usually employed for positive working presensitized plate, wipe-on plate or photo-resist, e.g., benzoquinone-1,2-diazide sulfonates or naphthoquinone-1,2-diazide sulfonates with polyhydoxy compounds, e.g., the ester from benzo-quinone-1,2-diazide sulfochloride and polyhydroxyphenyl~ the ester from naphthoquinone-1,2-diazide sulfochloride and pyrogallol acetone resin, or the ester from naphthoquinone-1,2-diazide sulfochloride and phenol-formaldehyde novolak resin, or complexes of diazonium compounds and inorganic or organic acids, e.g., a photosensitive complex of diazodi-phenylamine and phosphotungstic acid.
., .
- 4b -`:' ' An example of the rne~hod of introducing a cross-linked str~cture into such a light-solubilizable photosensitive compotmd, includes a method wherein reactive groups, e.g. hydroxyl and amino, contained in the said photosensitive compound are cross-linked with a polyfunctional cross-linking agent.
Examples of such cross-linking agents are poly:isocyanate compounds, e.g. paraphenylene diisocyanate, 2,~- or 2,6-toluene dlisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, or adducts thereof, and polyepoxy compounds, e.g. polyethylene glycol diglycidyl ethers, polypropylene glycol diglycidyl ethers, bisphenol A diglycidyl ether, and trimethyl-olpropane triglycidyl ether. It is necessary that the curing operation with these cross-linking agents be carried out under conditions under which the photosensitive substance will not lose its photosensitivity, usually at a temperature not higher than ~20C. To this end, a catalyst or the like is used.
Another method of rendering such light-solubilizable photosensitive compound difficult to dissolve or insoluble in a developer involves, for example, urethanizing, esterlfying or amidizing a functional group contained in the photosensitive compound. The compound to be reacted with such functional group of the photosensitive compound may be either a low molecular or relatively high molecular compound. Alternatively, a vinyl monomer may be graft-polymerized to the photosensitive compound.
A specially preferred photosensitive layer used in aspects of this invention is obtained by cross-linking or modifying a partial ester from naphthoquinone-1~2-diazide-5-sulfochloride and phenol-formaldehyde novolak resin with a poly- or mono-functional isocyanate.
Other components may be incorporated on the photosensitive layer with a view to improYing tlle film-forming property or the adhesion to the base substrate, or dyest~l~s for making image vislble _ 5 _ ` .
:
i -- 1 16~%6~
at the time of development or exposure, provid~d that such incorporation should not spoil the effect of aspects of this invention.
The thickness of the li~ht-releasing layer used in aspects of this invention is in the ranye of 0.1 to 100 ~u, preferably from 0.5 to 10 ~. A smaller thickness is likely to cause defects, e.g. the formation of pinholes at the time of coating, while a larger thickness is disadvantageous from the economic point of view.
The silicone rubber layer used in aspects of this invention consists maily of a linear organopolysiloxane of several thousand to several hundred thousand molecular weights having the following repeating unit:
~ R
Or R n wherein n is an integer not less than 1 and R i8 Cl to C10 alkyl, alkenyl or phenyl with 60% or more of R being preferably methyl gro~p_ Such a linear organopDlysiloxane may be mixed with an organic peroxide and heat-treated to give a scarcely cross-linked silicone rubber.
Also added to the linear organopolyslloxane is a cross-linking agent which is the so-called room temperature (low temperature) vulcanizing type used for silicone rubber, e.g. acetoxysilanes, ketoximosilanes, alkoxysilanes, aminosilanes and amidesilanes. Using these cross-linking agents in combination with a hydroxyl-terminated linear organopolysiloxane respectively a~ford deacetic-acid type, deoxime type, dealcohol-type, deamine type and deamide_type silicone rubbers. To these sillcone rubbers, in general, is further added a small amount of an organotin compound or
3~ the like as a catalyst.
1, %~
The thicknes~ o~ the ~lllcane rubber layer range8 froM
0.5 to 10~. A smaller thickness may cause problems ln point of printing endurance, while a larger thicknegs i8 not ~nly disadvantageous from the economic point of view but also i8 counter to one of ~he objects of the inventlon that the cell is to be made shallow, and further it becomes difficult to remove the silicone rubber layer at the time of development which leads to inferior lmage reproducibility.
In the planographic printing plate of aspects of this invention, the adhesion between the base substrate and the photosensitive layer and that between the photosensitive layer and the silicone rubber layer are so important for the fundamental plate performances, e.g. image reproducibility and printing endurance that, if required, an adhesive layer may be formed between the above layers, or an adhesion im-proving component may be incorporated in each of the above layers. Particularly for the bonding between the photosen-sitive layer and the silicone rubber layer, it is effective to provide therebetween a known silicone primer or silane coupling agent layer, or incorporate a silicone primer or silane coupling agent into the photosensitive layer or the silicone rubber layer.
~ The base substrate should be flexible enough to be set in a conventional planographic printing machine and be strong enough to withstand the load applied in printing, typlcal of which are metallic plates, e.g. aluminum, copper ana steel, plastic films, e.g. polyethylene terephthalate, and coateQ papexs. A further coating may be applied onto these sheets for the prevention of halation or for other objects, and the so-coated sheets may be used as the base substrate.
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1 1642~
A thin protective Eilm may be laminatf3d on the surface of thesilicone r~ber layer to protec-t the silicone rubber layer as the surface layer of the dry planographic printing plate constructed as above, or for other purposes.
The hereinabove-described dry planographic pr~nting plate based on aspects of this invention is manufactured, for example, in the following manner. First, a solution of a photosensitive-layer-forming composition is applied onto the base substrate by the use of a conventional coater, e.g. reverse roll coater, air knife coater or Mayer bar coater, or a rotary applicator, e.g., whirler, followed by drying and, if required, heat-curing. Then, if required after applying an adhesive layer onto the photo-sensitive layer in the same manner followed by drying, a silicone rubber solution is applied thereonto, also in the same manner, follo~!ed by heat treatment usually at a temperature of 100 to 120 for several minutes to allow curing to take place to a satisfactory extent to form a silicone rubber layer~ If necessary, the so-formed silicone rubber layer is covered with a protective film by means of a laminator or the like.
The dry planographic printing plate of aspects of this invention produced as described above is exposed to actinic light through a negative transpareny closely adhered to the plate in vacuo. The light source used for this exposure step should generate ablmdant ultraviolet rays (light), and mercury lamps, carbon arc lamps, xenone lamps, metal halide lamps or fluorescent lamps may be used as such light source.
Then,the plate, after exposure, is rubbed with a developing pad containing a developer whereby only the .~ . .
' .
28~
silicone rubber layer of the exposed portion is ~emoved, while the photsensitive layer which has been mads dif~icult to dissolve or insoluble in the developer by cross-linking or modifying remains without substantial reduction of its thickness, with the exposed surface of the photosensitive layer constituting an ink receiving portion.
Suitable developers which may be used in providing the plate of aspects of this invention comprise aliphatic hydrocarb-ons (e.~, hexane, heptane, gasoline, kerosene), aromatic hydrocarbons (e.g. toluene, xylene), or halogenated hydrocarbons te.g. trichlene), which are capable o~ swelling silicone rubber, and the following polar solvents incorporated therein:
~lcohols (e.g. methanol, ethanol); Ethers (e.g.
ethyl cellosolve, dioxane); Ketones (e.g. acetone, methyl ethyl ketone); Esters (e.g. ethyl acetate, -cellosolve acetate).
The principle of image formation by the light ` ~eleasing, photosens~tive layer in the plate of aspects of this invention is unknown, but is presumed to be based on the chan~e in adhesion of the photosensitive layer to the silicone rubber layer due to change in polarity of the photosensitive layer on exposure or change in swelling property of the photosensitlve layer against the developing solvent. The depth of the fine cell as an ink-recelving portion of the printing plate obtained in this manner is smaller by the thickness of the photosensitive layer than the depth of the cell in conventional negatlve working dry planographic prlnting plate in which the solubilized photosensitive layer of the e~posed area is dissolved off and at the sa~e time the overlying silicone ~bber layer is removed. '~e .
g :: :
ink receiving portion to be e~posed Inay be formed of a highly ink-receptive resin. For this reason, the use of the p~anographic printing plate of aspects of this inven-tion can afford an extremely good printed matter free from the so-called dot omission.
Furthermore, the image area constituted by the photosensitive layer as the surface layer is easily dyed with dyestuffs, while the non-image area constituted by the silicone rubber layer as the surface area is not dyed.
Therefore~ it is possible to inspect the printing plate with only the image area dyed. When it has become necessary to eliminate the ink receptivity of the image area concerned as a result of proofreading or the like, a sllicone rubber solution is applied to the portion concerned to cover the image area with a silicone rubber film. Since the photosensitive layer of the image area is particularly superior in the adhesion to the sili-cone rubber film formed on the eliminated portion, the latter portion also has an excellent printing ~2;
.: .
6 ~
endurance.
Workiny examples of aspects of this invention are given below to illustrate various aspects of this in-vention more in detail. The parts used therein are allparts by weight.
Example l (A) A solution of the following photosensitive layer forming composition was applied onto a chemical conversion coated aluminum plate (0.3 mm thick, a product of Sumitomo Light Metal Industries) followed by heat treatment for 2 minutes at 120 C, to form a 2.6 JU thick photosensitive layer:
(a) Naphthoquinone-1,2~diazide-5-sulfoester of phenol novolak resin t"Sumilightresin PR 50235," a product of Sumltomo Dure Co., Ltd.) with a percent esterification 44%100 parts (b~ 4,4-diphenylmethane dilsocyanate 20 parts (c) Dibutyl tln dilaurate 0.2 part (d) ~ethyl cellosolve acetate2000 parte A silicone rubber solution of the following compo-sition was then applied onto the photosensitive layer thus formed followed by heating for 2 minutes at 120 C to allow cure to take place, to form a 2.2~u thick silicone rubber layer:
~a) Dimethyl polysiloxane (molecular weigh~ about 80,000, hydroxylterminated) 100 parts tb) Ethyl triacetoxy silane ~ 5 parts (c) Dibutyl tin diacetate 0.2 part (d) ~-amlnopropyl triethoxy sllane 3 parts (e) Iso Par E 1650 parts~
, ~ .
~.
~ 16~26~
A negative film having dot image of 175 lines, was closely ad-- hered in vacuo in known manner to the prir,ting master plate thus obtained which was then exposed image-wise for 60 seconds at a ~istance of 1 m.
using a metal halide lamp. The plate was then il~nersed in a mixed ethanol/
ISOPAR E 20/80 solution and rubbed ln ghtly with a developiny pad, resulting in that the silicone rubber layer of the exposed area was rel~ved, allowing the surface of the photosensitive layer to be exposed, to give an image true to the original film.
The printing plate thus obtained was checked for the surface con-dition with h stylus-type surface roughness tester (known by the trade maxk of TALYSURF, a product of Teijin Shoji) to find that the surface of the photosensitive layer of the area exposed on development was very smooth and the thickness of the photosensitive layer was not reduced, which was 2.6 u.
(B) On the other hand, a photosensitive layer of the following com-position was formed on the same aluminum plate as that described above so that the thickness thereof was 2.6 u followed by heat -treatment for 2 minutes at 120C:
(a) Naphthoquinione-1,2-diazide-5-s~llfoester of phenol novolak resin (SUMILIGilTRESIN PR 50235, the trade mark of a product of Sumitomo Durez Co., Ltd.) with a percent esterification 44%.
Then, the same silicone rubber layer as that described in the above (A) was formed on the so-formed photosensitive layer so as to give the same thickness, followed by heat treatment for 2 minutes at 120C.
Subsequent exposure and development in the same manner as in the above (A) allowed the photosensitive layer of the exposed area to be dissolved off and at the same time the overlying silicone rubber layer to be removed leaving an exposed aluminum plate, to give a printing pla-te.
.lB
6 ~
The printing plates obtained in the above (A) and ~B) were each attached to an offset press (known by the trade mark of KO~IORI SPRINT 2 colour) and a printing was made using AQUAI,ESS ST CYAN (the trade mark of a product of Toyo Ink Mfg. Co.) without using dampening water. The print-ing was made on levels from Z.0 to 0.7 of the optical densit~ of the solid portion on the printed matter, while the adhesion of ink in the high-light area (dot diameter 50-70 p) was observed with the eyes through a magnifier (50X). As a result, the optical density of the solid portion at which the adhesion of ink became poor tsomewhat or complete omission of dot) was found to be 0.8 to 0.9 in the plate (A) and 1.3 to 1.4 in the plate (B). In the same amount of ink, the plate (A) exhibited a remarka-ble improvement in the adhesion of ink to the dot area.
Example 2 A resol resin (known by the trade mark of S~ILIGHTRESIN PC-l, a product of Sumitomo Durez Co., Ltd.) was applied onto a 0.24 mm thick aluminum plate (a product of Sumitomo Light Metal Industries) so as to give a 2JU thickness, followed by heat treatment at 180C for 3 minutes to allow cure to take place, to give a base substrate. Then, a solution of the following photosensitive layer composition was applied onto the base substrate and was cured by heating at 120C for 2 minutes to form a 2.4~u thick photosensitve layer:
B
Naphthoquinone-1,2-diazide-5-sulf oes ter of phenol novolak resin tthe one described in ~xample 1) 100 parts (b) 2,5-toluene d~socyanate 20 parts ~c) Dibutyl ti~ dilaurate 0.2 part (d) Dioxane 2000 parts Then, a silicone rubber solution of the following composition ~as applied onto the photosensitive layer and was eured by heating at 120C for 2 minutes to form a 2.~u thick silicone rubber layer:
(a) Dimethyl polysiloxane (molecular weight 80,000, hydroxylterminated) 100 parts (b) Vinyl tri(methylethylketoximo)sllane8 parts (c~ Dibutyl tin diacetate . 0.2 part (d) r-[N- ~-aminoethyl)amino~propyl trimethoxy silane 2.5 partæ
(e) ISOPAR E 1800 parts The printing master plate thus obtained was exposed for 60 seconds at a distance of 1 meter using a metal halide lamp through a negative film having dot image of 150 lines adhered closely in vacuo 2~ to the plate. The plate was then immerRed in a developer (ISopAR E/
ethanol, 9/1) containing a dye (oil Blue A) and rubbed lightly with a developing pad, resulting in that only the silicone rubber layer of the exposed srea was removéd and there was obtained a printing plate having an exposed dyed photosensltive layer exactly reproducing the image of the negative film.
~.. ~ . . .
' ':
. .
.
:
~ 16~26~
Example 3 To 30 ml. of dry dioxane were added, under N2 gas stream, 10 g. of phenyl isocyanate and 20 mg. of dibutyl tin dilaurate, then 7 g. of naphthoquinone-l, 2-diazide S-.sulfoester of phenol novolak with a percent esterification 43% was added with stirring. The stirring was continued for 3 hours at room temperature. Then after standing overnight, 1 ml. of water was added to allow the remaining phenyl isocyanate to decompose. The reaction mixture was filtered to remove the precipitate. m e filtrate was then put into a large excess of water to allow precipitation to take place, followed by filtration and drying to give a yellow powder.
m e naphthoquinone-l, 2-diazide-5-sulfoester of phenol novolak - resin thus modified wi-th phenyl isocyanate was dissolved in dioxane to pre-pare a 5 wt.~ solution. This solution was applied onto a 0.3mm thick chemical conversion coated aluminum plate and then dried to give a 2.2 ~
thick photosensitive layer, on which layer was then applied a silicon rub-ber layer in the same manner as in Example 2. The printing master plate thereby obtained was exposed for 60 seconds at a distance of 1 meter using a metal halide lamp through a negative film having dot image of 150 lines adhered closely in vauo to the plate. The plate was then soaked in a mixed ISOPAR E/ethanol (9/1) solution and rubbed with a developing pad, re-sulting in that only the silicone rubber layer of the exposed area was re-moved leaving exposed photosensitive layer, which constituted a true image to the original film.
The printing plate thus obtained was checked for the surface con-dition with a stylus type surface roughness tester (TALYSURF, a product of Teijin Shoji) to find that the surface of the photosensitive layer of the area exposed on development was smooth and the thickness of the photo-sensitive layer was 2.2J~.
~ 16~6~
Example 4 Vsing each of the printing plates obtained in Exarnples l~A), 2 and 3, a printing was made with AQUALESS ST MAGENTA (the trade mark, a product of Toyo Ink Mfg., Co) without using dampening water by means of an offset press (known by the trade mark of DAVIDSON DUALITH 700).
As a result, all the printing plates afforded beautiful printed mat~ers and even after printing 20,000, 10,000 and 10,000 copies respectively, their surfaces were free from damage, showing capability cJf further printing.
.
1, %~
The thicknes~ o~ the ~lllcane rubber layer range8 froM
0.5 to 10~. A smaller thickness may cause problems ln point of printing endurance, while a larger thicknegs i8 not ~nly disadvantageous from the economic point of view but also i8 counter to one of ~he objects of the inventlon that the cell is to be made shallow, and further it becomes difficult to remove the silicone rubber layer at the time of development which leads to inferior lmage reproducibility.
In the planographic printing plate of aspects of this invention, the adhesion between the base substrate and the photosensitive layer and that between the photosensitive layer and the silicone rubber layer are so important for the fundamental plate performances, e.g. image reproducibility and printing endurance that, if required, an adhesive layer may be formed between the above layers, or an adhesion im-proving component may be incorporated in each of the above layers. Particularly for the bonding between the photosen-sitive layer and the silicone rubber layer, it is effective to provide therebetween a known silicone primer or silane coupling agent layer, or incorporate a silicone primer or silane coupling agent into the photosensitive layer or the silicone rubber layer.
~ The base substrate should be flexible enough to be set in a conventional planographic printing machine and be strong enough to withstand the load applied in printing, typlcal of which are metallic plates, e.g. aluminum, copper ana steel, plastic films, e.g. polyethylene terephthalate, and coateQ papexs. A further coating may be applied onto these sheets for the prevention of halation or for other objects, and the so-coated sheets may be used as the base substrate.
.. ,. -`
. ' . . ~ " ` `
1 1642~
A thin protective Eilm may be laminatf3d on the surface of thesilicone r~ber layer to protec-t the silicone rubber layer as the surface layer of the dry planographic printing plate constructed as above, or for other purposes.
The hereinabove-described dry planographic pr~nting plate based on aspects of this invention is manufactured, for example, in the following manner. First, a solution of a photosensitive-layer-forming composition is applied onto the base substrate by the use of a conventional coater, e.g. reverse roll coater, air knife coater or Mayer bar coater, or a rotary applicator, e.g., whirler, followed by drying and, if required, heat-curing. Then, if required after applying an adhesive layer onto the photo-sensitive layer in the same manner followed by drying, a silicone rubber solution is applied thereonto, also in the same manner, follo~!ed by heat treatment usually at a temperature of 100 to 120 for several minutes to allow curing to take place to a satisfactory extent to form a silicone rubber layer~ If necessary, the so-formed silicone rubber layer is covered with a protective film by means of a laminator or the like.
The dry planographic printing plate of aspects of this invention produced as described above is exposed to actinic light through a negative transpareny closely adhered to the plate in vacuo. The light source used for this exposure step should generate ablmdant ultraviolet rays (light), and mercury lamps, carbon arc lamps, xenone lamps, metal halide lamps or fluorescent lamps may be used as such light source.
Then,the plate, after exposure, is rubbed with a developing pad containing a developer whereby only the .~ . .
' .
28~
silicone rubber layer of the exposed portion is ~emoved, while the photsensitive layer which has been mads dif~icult to dissolve or insoluble in the developer by cross-linking or modifying remains without substantial reduction of its thickness, with the exposed surface of the photosensitive layer constituting an ink receiving portion.
Suitable developers which may be used in providing the plate of aspects of this invention comprise aliphatic hydrocarb-ons (e.~, hexane, heptane, gasoline, kerosene), aromatic hydrocarbons (e.g. toluene, xylene), or halogenated hydrocarbons te.g. trichlene), which are capable o~ swelling silicone rubber, and the following polar solvents incorporated therein:
~lcohols (e.g. methanol, ethanol); Ethers (e.g.
ethyl cellosolve, dioxane); Ketones (e.g. acetone, methyl ethyl ketone); Esters (e.g. ethyl acetate, -cellosolve acetate).
The principle of image formation by the light ` ~eleasing, photosens~tive layer in the plate of aspects of this invention is unknown, but is presumed to be based on the chan~e in adhesion of the photosensitive layer to the silicone rubber layer due to change in polarity of the photosensitive layer on exposure or change in swelling property of the photosensitlve layer against the developing solvent. The depth of the fine cell as an ink-recelving portion of the printing plate obtained in this manner is smaller by the thickness of the photosensitive layer than the depth of the cell in conventional negatlve working dry planographic prlnting plate in which the solubilized photosensitive layer of the e~posed area is dissolved off and at the sa~e time the overlying silicone ~bber layer is removed. '~e .
g :: :
ink receiving portion to be e~posed Inay be formed of a highly ink-receptive resin. For this reason, the use of the p~anographic printing plate of aspects of this inven-tion can afford an extremely good printed matter free from the so-called dot omission.
Furthermore, the image area constituted by the photosensitive layer as the surface layer is easily dyed with dyestuffs, while the non-image area constituted by the silicone rubber layer as the surface area is not dyed.
Therefore~ it is possible to inspect the printing plate with only the image area dyed. When it has become necessary to eliminate the ink receptivity of the image area concerned as a result of proofreading or the like, a sllicone rubber solution is applied to the portion concerned to cover the image area with a silicone rubber film. Since the photosensitive layer of the image area is particularly superior in the adhesion to the sili-cone rubber film formed on the eliminated portion, the latter portion also has an excellent printing ~2;
.: .
6 ~
endurance.
Workiny examples of aspects of this invention are given below to illustrate various aspects of this in-vention more in detail. The parts used therein are allparts by weight.
Example l (A) A solution of the following photosensitive layer forming composition was applied onto a chemical conversion coated aluminum plate (0.3 mm thick, a product of Sumitomo Light Metal Industries) followed by heat treatment for 2 minutes at 120 C, to form a 2.6 JU thick photosensitive layer:
(a) Naphthoquinone-1,2~diazide-5-sulfoester of phenol novolak resin t"Sumilightresin PR 50235," a product of Sumltomo Dure Co., Ltd.) with a percent esterification 44%100 parts (b~ 4,4-diphenylmethane dilsocyanate 20 parts (c) Dibutyl tln dilaurate 0.2 part (d) ~ethyl cellosolve acetate2000 parte A silicone rubber solution of the following compo-sition was then applied onto the photosensitive layer thus formed followed by heating for 2 minutes at 120 C to allow cure to take place, to form a 2.2~u thick silicone rubber layer:
~a) Dimethyl polysiloxane (molecular weigh~ about 80,000, hydroxylterminated) 100 parts tb) Ethyl triacetoxy silane ~ 5 parts (c) Dibutyl tin diacetate 0.2 part (d) ~-amlnopropyl triethoxy sllane 3 parts (e) Iso Par E 1650 parts~
, ~ .
~.
~ 16~26~
A negative film having dot image of 175 lines, was closely ad-- hered in vacuo in known manner to the prir,ting master plate thus obtained which was then exposed image-wise for 60 seconds at a ~istance of 1 m.
using a metal halide lamp. The plate was then il~nersed in a mixed ethanol/
ISOPAR E 20/80 solution and rubbed ln ghtly with a developiny pad, resulting in that the silicone rubber layer of the exposed area was rel~ved, allowing the surface of the photosensitive layer to be exposed, to give an image true to the original film.
The printing plate thus obtained was checked for the surface con-dition with h stylus-type surface roughness tester (known by the trade maxk of TALYSURF, a product of Teijin Shoji) to find that the surface of the photosensitive layer of the area exposed on development was very smooth and the thickness of the photosensitive layer was not reduced, which was 2.6 u.
(B) On the other hand, a photosensitive layer of the following com-position was formed on the same aluminum plate as that described above so that the thickness thereof was 2.6 u followed by heat -treatment for 2 minutes at 120C:
(a) Naphthoquinione-1,2-diazide-5-s~llfoester of phenol novolak resin (SUMILIGilTRESIN PR 50235, the trade mark of a product of Sumitomo Durez Co., Ltd.) with a percent esterification 44%.
Then, the same silicone rubber layer as that described in the above (A) was formed on the so-formed photosensitive layer so as to give the same thickness, followed by heat treatment for 2 minutes at 120C.
Subsequent exposure and development in the same manner as in the above (A) allowed the photosensitive layer of the exposed area to be dissolved off and at the same time the overlying silicone rubber layer to be removed leaving an exposed aluminum plate, to give a printing pla-te.
.lB
6 ~
The printing plates obtained in the above (A) and ~B) were each attached to an offset press (known by the trade mark of KO~IORI SPRINT 2 colour) and a printing was made using AQUAI,ESS ST CYAN (the trade mark of a product of Toyo Ink Mfg. Co.) without using dampening water. The print-ing was made on levels from Z.0 to 0.7 of the optical densit~ of the solid portion on the printed matter, while the adhesion of ink in the high-light area (dot diameter 50-70 p) was observed with the eyes through a magnifier (50X). As a result, the optical density of the solid portion at which the adhesion of ink became poor tsomewhat or complete omission of dot) was found to be 0.8 to 0.9 in the plate (A) and 1.3 to 1.4 in the plate (B). In the same amount of ink, the plate (A) exhibited a remarka-ble improvement in the adhesion of ink to the dot area.
Example 2 A resol resin (known by the trade mark of S~ILIGHTRESIN PC-l, a product of Sumitomo Durez Co., Ltd.) was applied onto a 0.24 mm thick aluminum plate (a product of Sumitomo Light Metal Industries) so as to give a 2JU thickness, followed by heat treatment at 180C for 3 minutes to allow cure to take place, to give a base substrate. Then, a solution of the following photosensitive layer composition was applied onto the base substrate and was cured by heating at 120C for 2 minutes to form a 2.4~u thick photosensitve layer:
B
Naphthoquinone-1,2-diazide-5-sulf oes ter of phenol novolak resin tthe one described in ~xample 1) 100 parts (b) 2,5-toluene d~socyanate 20 parts ~c) Dibutyl ti~ dilaurate 0.2 part (d) Dioxane 2000 parts Then, a silicone rubber solution of the following composition ~as applied onto the photosensitive layer and was eured by heating at 120C for 2 minutes to form a 2.~u thick silicone rubber layer:
(a) Dimethyl polysiloxane (molecular weight 80,000, hydroxylterminated) 100 parts (b) Vinyl tri(methylethylketoximo)sllane8 parts (c~ Dibutyl tin diacetate . 0.2 part (d) r-[N- ~-aminoethyl)amino~propyl trimethoxy silane 2.5 partæ
(e) ISOPAR E 1800 parts The printing master plate thus obtained was exposed for 60 seconds at a distance of 1 meter using a metal halide lamp through a negative film having dot image of 150 lines adhered closely in vacuo 2~ to the plate. The plate was then immerRed in a developer (ISopAR E/
ethanol, 9/1) containing a dye (oil Blue A) and rubbed lightly with a developing pad, resulting in that only the silicone rubber layer of the exposed srea was removéd and there was obtained a printing plate having an exposed dyed photosensltive layer exactly reproducing the image of the negative film.
~.. ~ . . .
' ':
. .
.
:
~ 16~26~
Example 3 To 30 ml. of dry dioxane were added, under N2 gas stream, 10 g. of phenyl isocyanate and 20 mg. of dibutyl tin dilaurate, then 7 g. of naphthoquinone-l, 2-diazide S-.sulfoester of phenol novolak with a percent esterification 43% was added with stirring. The stirring was continued for 3 hours at room temperature. Then after standing overnight, 1 ml. of water was added to allow the remaining phenyl isocyanate to decompose. The reaction mixture was filtered to remove the precipitate. m e filtrate was then put into a large excess of water to allow precipitation to take place, followed by filtration and drying to give a yellow powder.
m e naphthoquinone-l, 2-diazide-5-sulfoester of phenol novolak - resin thus modified wi-th phenyl isocyanate was dissolved in dioxane to pre-pare a 5 wt.~ solution. This solution was applied onto a 0.3mm thick chemical conversion coated aluminum plate and then dried to give a 2.2 ~
thick photosensitive layer, on which layer was then applied a silicon rub-ber layer in the same manner as in Example 2. The printing master plate thereby obtained was exposed for 60 seconds at a distance of 1 meter using a metal halide lamp through a negative film having dot image of 150 lines adhered closely in vauo to the plate. The plate was then soaked in a mixed ISOPAR E/ethanol (9/1) solution and rubbed with a developing pad, re-sulting in that only the silicone rubber layer of the exposed area was re-moved leaving exposed photosensitive layer, which constituted a true image to the original film.
The printing plate thus obtained was checked for the surface con-dition with a stylus type surface roughness tester (TALYSURF, a product of Teijin Shoji) to find that the surface of the photosensitive layer of the area exposed on development was smooth and the thickness of the photo-sensitive layer was 2.2J~.
~ 16~6~
Example 4 Vsing each of the printing plates obtained in Exarnples l~A), 2 and 3, a printing was made with AQUALESS ST MAGENTA (the trade mark, a product of Toyo Ink Mfg., Co) without using dampening water by means of an offset press (known by the trade mark of DAVIDSON DUALITH 700).
As a result, all the printing plates afforded beautiful printed mat~ers and even after printing 20,000, 10,000 and 10,000 copies respectively, their surfaces were free from damage, showing capability cJf further printing.
.
Claims (19)
1. A negative working presensitized printing plate for use in dry planography, which comprises:
(1) a base substrate, (2) an oleophilic photosensitive layer secured to, and over-lying, said base substrate, and (3) an ink repelling silicone rubber layer secured to, and overlying, said photosensitive layer, said photosensitive layer being substantially insoluble in a developer both before and after the exposure to the actinic light, and being capable of releasing said silicone rubber layer in a selected area to be exposed to the actinic light, and said silicone rubber layer being capable of being removed in said exposed image area by a developer.
(1) a base substrate, (2) an oleophilic photosensitive layer secured to, and over-lying, said base substrate, and (3) an ink repelling silicone rubber layer secured to, and overlying, said photosensitive layer, said photosensitive layer being substantially insoluble in a developer both before and after the exposure to the actinic light, and being capable of releasing said silicone rubber layer in a selected area to be exposed to the actinic light, and said silicone rubber layer being capable of being removed in said exposed image area by a developer.
2. A negative working presensitized planographic printing plate for use in dry planography, comprising: an image area constituted by a photosensitive layer overlying a base substrate; and a non-image area con-stituted by a silicone rubber layer overlying said photosensitive layer.
3. The plate as defined in claim 1, in which said photosensitive -layer is made difficult to dissolve or insoluble in the developer by cross-linking a quinonediazide compound with a polyfunctional compound.
4. The plate as defined in claim 2, in which said photosensitive layer is made difficult to dissolve or insoluble in the developer by cross-linking a quinonediazide compound with a polyfunctional compound.
5. The plate as defined in claim 3 wherein said quinonediazide compound is naphthoquinone-1,2-diazide sulfonate with a polyhydroxy com-pound.
6. The plate as defined in claim 4 wherein said quinonediazide compound is naphthoquinone-1,2-diazide sulfonate with a polyhydroxy com-pound.
7. The plate as defined in claim 3 wherein said quinonediazlde compound is naphthoquinone-1,2-diazide sulfonate with a phenol-formalde-hyde novolak resin.
8. The plate as defined in claim 4 wherein said quinonediazide compound is naphthoquinone-1,2-diazide sulfonate with a phenol-formalde-hyde novolak resin.
9. The plate as defined in claims 1 or 2, in which said photo-sensitive layer is made difficult to dissolve or insoluble in the developer by cross-linking a quinonediazide compound with a polyisocyanate compound.
10. The plate as defined in claims 1 or 2, in which said photo-sensitive layer is made difficult to dissolve or insoluble in the developer by cross-linking a quinonediazide compound with a polyepoxy compound.
11. The plate as defined in claims 1 or 2, in which said photosensitive layer is made difficult to dissolve or insoluble in the developer by urethanizing a quinonediazide compound with a monoisocyanate.
12. The plate as defined in claims 1 or 2, in which said photosensitive layer is made difficult to dissolve or insoluble in the developer by esterifying a quinonediazide compound.
13. The plate as defined in claims 1 or 2, in which said photosensitive layer is made difficult to dissolve or insoluble in the developer by amidizing a quinonediazide compound.
14. The plate as defined in claims 1 or 2, in which said photosensitive layer is made difficult to dissolve or insoluble in the developer by graft polymerizing a quinonediazide compound with a vinyl monomer.
15. The plate as defined in claims 1 or 2, in which the thickness of said photosensitive layer is in the range of from 0.1 to 100µ.
16. The plate as defined in claims 1 or 2, in which said silicone rubber layer comprises a cross-linked diorganopolysiloxane obtained by curing diorganopolysiloxane having the following repeating unit:
where n is an integer not less than 1 and R, which may be alike or dif-ferent, is each C1 to C10 alkyl, alkenyl or phenyl with 60% or more of R
being methyl group.
where n is an integer not less than 1 and R, which may be alike or dif-ferent, is each C1 to C10 alkyl, alkenyl or phenyl with 60% or more of R
being methyl group.
17. The plate as defined in claims 1 or 2, in which said silicone rubber layer comprises a cross-linked diorganopolysiloxane obtained by curing diorganopolysiloxane having the following repeating unit:
where n is an integer not less than 1 and R, which may be alike or differ-ent, is each C1 to C10 alkyl, alkenyl or phenyl with 60% or more of R
being methyl group, and in which the thickness of said silicone rubber layer is in the range of from 0.5 to 10µ.
where n is an integer not less than 1 and R, which may be alike or differ-ent, is each C1 to C10 alkyl, alkenyl or phenyl with 60% or more of R
being methyl group, and in which the thickness of said silicone rubber layer is in the range of from 0.5 to 10µ.
18. Method of making a negative working presensitized planographic printing plate for use in dry planography, which method comprises: image-wise exposing a printing master, said printing master comprising a base substrate, a photosensitive layer being difficult to dissolve or insoluble in a developer and overlying said base substrate and a silicone rubber layer overlying said photosensitive layer; and subsequently treating the exposed printing master with said developer to allow only the exposed image areas of said silicone rubber layer to be removed.
19. A negative working presensitized printing plate for use in dry planography, which comprises:
(1) a base substrate;
(2) an oleophilic photosensitive layer secured to and overlying said base substrate; and (3) an ink repelling silicone rubber layer secured to and overlying said photosensitive layer;
said photosensitive layer further comprising a component selected from the group consisting of a quinonediazide cross-linked with a polyfunc-tional compound, a quinonediazide urethanized with a monoisocyanate, an esterified quinonediazide, an amidized quinonediazide, a quinonediazide graft polymerized with a vinyl monomer, so that said photosensitive layer is substantially insoluble in a developer, capable of releasing said silicone rubber and constituting an image area in a selected area to be exposed to the actinic light, and so that said silicone rubber layer is capable of being removed in said exposed image area by said developer and constituting a non-image area in an area unexposed to the actinic light.
(1) a base substrate;
(2) an oleophilic photosensitive layer secured to and overlying said base substrate; and (3) an ink repelling silicone rubber layer secured to and overlying said photosensitive layer;
said photosensitive layer further comprising a component selected from the group consisting of a quinonediazide cross-linked with a polyfunc-tional compound, a quinonediazide urethanized with a monoisocyanate, an esterified quinonediazide, an amidized quinonediazide, a quinonediazide graft polymerized with a vinyl monomer, so that said photosensitive layer is substantially insoluble in a developer, capable of releasing said silicone rubber and constituting an image area in a selected area to be exposed to the actinic light, and so that said silicone rubber layer is capable of being removed in said exposed image area by said developer and constituting a non-image area in an area unexposed to the actinic light.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP156871/1979 | 1979-12-05 | ||
| JP15687179A JPS5680046A (en) | 1979-12-05 | 1979-12-05 | Lithographic plate requiring no dampening water and its manufacture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1164267A true CA1164267A (en) | 1984-03-27 |
Family
ID=15637205
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000365953A Expired CA1164267A (en) | 1979-12-05 | 1980-12-02 | Dry planographic printing plate and preparation thereof |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS5680046A (en) |
| CA (1) | CA1164267A (en) |
| DE (1) | DE3045979A1 (en) |
| FR (1) | FR2471622B1 (en) |
| GB (1) | GB2064803B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5917552A (en) * | 1982-07-21 | 1984-01-28 | Toray Ind Inc | Method for processing image forming laminate |
| JPS59202467A (en) * | 1983-05-02 | 1984-11-16 | Toray Ind Inc | Negative type lithographic plate requiring no dampening water |
| JPS6029750A (en) * | 1983-06-23 | 1985-02-15 | Toray Ind Inc | Lithographic plate requiring no dampening water |
| JPS60169852A (en) * | 1984-02-14 | 1985-09-03 | Fuji Photo Film Co Ltd | Manufacture of negative type photosensitive lithographic plate requiring no dampening water |
| JPS61241759A (en) * | 1985-04-18 | 1986-10-28 | Toray Ind Inc | Lithographic plate requiring no water |
| JPH07253661A (en) * | 1986-04-11 | 1995-10-03 | Toray Ind Inc | Waterless planographic printing plate |
| JPH07104598B2 (en) * | 1986-04-11 | 1995-11-13 | 東レ株式会社 | Waterless planographic printing plate |
| JP2507348B2 (en) * | 1986-09-18 | 1996-06-12 | 東レ株式会社 | Waterless planographic printing plate |
| JP2507347B2 (en) * | 1986-09-18 | 1996-06-12 | 東レ株式会社 | Waterless planographic printing plate |
| JPH07101306B2 (en) * | 1987-07-01 | 1995-11-01 | 東レ株式会社 | Waterless planographic printing plate |
| EP0938028A1 (en) * | 1998-02-24 | 1999-08-25 | Toray Industries, Inc. | A precursor of waterless planographic printing plates |
| CN100566548C (en) * | 2005-03-18 | 2009-12-09 | 洋马株式会社 | Raising apparatus |
| DE102014001970A1 (en) * | 2014-02-13 | 2015-08-13 | Heidelberger Druckmaschinen Ag | Assembly of a sheet or web-shaped substrate processing machine |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS564908B2 (en) * | 1972-03-21 | 1981-02-02 | ||
| JPS5426923B2 (en) * | 1972-03-21 | 1979-09-06 | ||
| JPS5539825B2 (en) * | 1972-05-12 | 1980-10-14 | ||
| JPS5612860B2 (en) * | 1972-10-05 | 1981-03-25 | ||
| JPS4983006A (en) * | 1972-12-15 | 1974-08-09 | ||
| GB1489308A (en) * | 1974-03-18 | 1977-10-19 | Scott Paper Co | Laser imagable dry planographic printing plate blank |
| JPS53131797A (en) * | 1977-04-21 | 1978-11-16 | Stanley Electric Co Ltd | Method of indicating position of transmission of vehicle |
| JPS5555344A (en) * | 1978-10-20 | 1980-04-23 | Toray Ind Inc | Lithographic printing plate |
| GB2034911B (en) * | 1978-10-26 | 1983-02-09 | Toray Industries | Dry planographic printing plate |
-
1979
- 1979-12-05 JP JP15687179A patent/JPS5680046A/en active Granted
-
1980
- 1980-12-02 CA CA000365953A patent/CA1164267A/en not_active Expired
- 1980-12-03 GB GB8038753A patent/GB2064803B/en not_active Expired
- 1980-12-05 FR FR8025920A patent/FR2471622B1/en not_active Expired
- 1980-12-05 DE DE19803045979 patent/DE3045979A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| GB2064803B (en) | 1984-06-06 |
| JPS5680046A (en) | 1981-07-01 |
| DE3045979A1 (en) | 1981-09-03 |
| JPS6154222B2 (en) | 1986-11-21 |
| DE3045979C2 (en) | 1990-12-06 |
| FR2471622A1 (en) | 1981-06-19 |
| FR2471622B1 (en) | 1987-03-06 |
| GB2064803A (en) | 1981-06-17 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |