CA1154291A - Modifying a surprint proof having a photosensitive tacky layer by exposure through a screen tint - Google Patents
Modifying a surprint proof having a photosensitive tacky layer by exposure through a screen tintInfo
- Publication number
- CA1154291A CA1154291A CA000386426A CA386426A CA1154291A CA 1154291 A CA1154291 A CA 1154291A CA 000386426 A CA000386426 A CA 000386426A CA 386426 A CA386426 A CA 386426A CA 1154291 A CA1154291 A CA 1154291A
- Authority
- CA
- Canada
- Prior art keywords
- tacky
- carrier particles
- particulate material
- layer
- process according
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
- B41M7/02—Dusting, e.g. with an anti-offset powder for obtaining raised printing such as by thermogravure ; Varnishing
-
- 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
- G03F3/00—Colour separation; Correction of tonal value
- G03F3/10—Checking the colour or tonal value of separation negatives or positives
- G03F3/103—Checking the colour or tonal value of separation negatives or positives using tonable photoresist or photopolymerisable systems
-
- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/28—Processing photosensitive materials; Apparatus therefor for obtaining powder images
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/151—Matting or other surface reflectivity altering material
Abstract
Title PROCESS FOR SURFACE IMPROVEMENT
OF SURPRINT PROOF
Abstract of the Invention Process for modifying a tacky surface of a multilayer negative-working surprint proof having a photosensitive tacky layer as the outer layer which comprises exposing the tacky layer through a halftone screen tint, e.g., having a tint value of 25 to 75 percent, and applying an admixture of particulate material and carrier particles and removing excess particulate material and the carrier particles from the tacky surface. The ratio of average particle diameter of the carrier particles to average particle diameter of the particulate material is greater than 2 and the weight ratio of particulate material to carrier particles is less than 1. A durable matte finish is obtained that is nonblocking, is capable of being written on, and is noncracking over extended storage periods.
OF SURPRINT PROOF
Abstract of the Invention Process for modifying a tacky surface of a multilayer negative-working surprint proof having a photosensitive tacky layer as the outer layer which comprises exposing the tacky layer through a halftone screen tint, e.g., having a tint value of 25 to 75 percent, and applying an admixture of particulate material and carrier particles and removing excess particulate material and the carrier particles from the tacky surface. The ratio of average particle diameter of the carrier particles to average particle diameter of the particulate material is greater than 2 and the weight ratio of particulate material to carrier particles is less than 1. A durable matte finish is obtained that is nonblocking, is capable of being written on, and is noncracking over extended storage periods.
Description
Title PROCESS FOR SURFACE IMPROV~ENT
OF SURPRINT PROOF
Description 5Technical Field This invention relates to a process for modifying the surface oE a surprint proof. More particularly, this invention relates to a process for modifying a tacky photosensitive outer layer of a negative-working surprint proof by exposing the tacky photosensitive layer through a screen tin~ and applying an admixture of particulate material and carrier particles to the exposed layer.
Background Art . .
15Photosensitive materials used in the preparation of surprint color proofs are o~ the positive-working or negative-working types. A
negative-working process for preparing surprint proofs is described in Cohen and Fan U.S. Patent 4,174,216. Negative-working elements useful in the nega~ive-working process comprise a support, a tacky, nonphotosensitive con~iguous layer, a photohardena~le - photoadherent layer and a s~rippable cover sheet.
After imagewise exposure to actinic radiation the 25 cover sheet is peeled away together with the exposed arèas of the photoadherent layer revealing the tacky contiguous layer beneath. The photoadherent layer in the unexposed image areas remains as a resist over the complementary portions of the con~iguous layer.
30 The tacky contiguous l~yer revealed in the exposed image areas is then toned with pigment. Layers toned with different pigments can be applied in registration over one another to form multilayer surprint color proofs. A tacky photosensitive layer PD-1875 35 generally is present as the outer layer of the proof. Dependent on the thickness of the layers, the proof may exhibit a pronounced undesirable three-dimensional effect. The multilayer surprint proofs having a positive-working photosensitive outer layer upon ageing exhibit cracks or crazes ln the surface thereof.
Methods are known by which negative-working materials can be provided with matte finishes.
Sprays have been used containing delustering agents but are messy, involve hazardous, flammable sprays, often do not cover the layer properly, yield a poor matte finish and the solvents may attack the image-forming layer. An advantageous process for providing a matte finish on negative-working multicolor surprint proofs is described and claimed in Cohen and Fan U.S. Patent 4 286 046 issued 1981 August 25. It was found by Cohen and Fan that by applying at least one layer of colloidal silica from a substantially aqueous dispersion and drying the layer to a dry coating weight of at least 20 mg/dm2 the three-dimensional effective is eliminated, and ;~ the surprint surface is hard and nonblocking, i.e., surfaces that are brought in conta~t therewith do not adhere. The wet methods for applying the matte finish are disadvantageous for the color proofer since a coater and the necessary solutions are .~ :
required with the inherent storage and cleanup problems. It is thereo~e desired that a method not requiring liquid or aqueous solutions be provided whereby the degree of matte of a tacky surface on a multilayer negative-working surprint proof can be effectively controlled, the three-dimensional efect be eliminated, a durable, nonblockiny surface be provided, and the cracking or crazing properties of the proof be improved.
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Disclosure of the Invention In accordance with this invention there isprovided in a process for modifying a tacky surface of a surprint multicolor proof having at least two non-planar, nonsilver halide, negative-working colored photoimaged elements sequentially honded to a support, and a photosensitive tacky layer present as the outer layer of the proof which comprises;
~1~ applying to the tacky surface an admixture of particulate material and carrier particles, the ratio in the admixture of the average;particle diameter of carrier particles to that of the particulate material in the admixture being greater than 2 and the weight ratio;of ~ ;
particulate material to carrier particles being less than 1, and (Z) removing excess particulate material and the car~ier particles ~rom the tacky surface, the improvement wherein prior to application to the tacky surface of the admixture of prticulate material and carrier particles the~photosensitive taaXy layer is exposed through a screen tint.
In practicing the process of the invention the tacky surface of the negative-working surpr~int proof that is modified and improved is a photosensi-tive tacky layer of a positive-workin~ photoharden-- able element. Tacky positive-working photoharden- -able elements (photohardenable layer between two removable films) are described, for example, in U.S.
Patent 3,649,26~. Positive-working elements ;are those wherein the photosensitive layer becomes hardened and nontacky in the exposed imaged areas and remains tacky in the unexposed areas. Generally the photohardenable layer contains at least one :
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' ~
~5~
free-radical initiated, chain-propagating, addition polymerizable compound containing at least one terminal ethylenic group, and an addition polymerization initiator activatable by actinic radiation, and optionally a compatible macromolecular organic polymeric binder. The tacky positive-wo king photohardenable element, after removal of one film, is present over the negative-working surprint proof, for example, of the type described in U.S.
Patent 4,174,216.
Negative-working surprint elements are elements wherein at least two photosensitive elements that have been imaged and colored with different colorants (nonplanar, nonsilver halide, colored, 15 photoimaged elements) are sequentially laminated or bonded to a suitable support surface, e.g., paper, film, e~c. In forming a surprint element, the cover sheet and any sheet support present in the photosensitive elements are removed. Preferred negative-working elements comprise, in order from top to bottom, (1) a ~trippable cover shee~, (2) a photoadheren~ layer comprising a material with ethylenically unsaturated or benzophenone ~ype groups, which is generally nontacky, (3) a tonable organic contiguous layer, e.g., a tacky, nonphotosensitivè elastomeric layer which is tonable by application of particulate material, and optionally (4) a sheet support. A positive-working photohardenable element, 2S described above is applied to the outermost colored photoimaged element of the surprint element.
Generally, the surprint element has over its support four imaged colored photopolymer elements, e.g., yellow, magenta, cyan, black, and an optional fifth nonimaged photopolymer element. Colorants and toners used in preparing the surprints are described in U.S. Patents 3,620,726, 3,909,282 and 4,304,843.
Ater the negative-working multicolor surprint proof with the positive-working photohardenable element present thereon is prepared, the surprint proof is exposed through a screen tint as described more fully below, the protective film of ` the exposed positive-workiny e}ement is removed and an aclmixture of particulate material and carrier particles~ lS applied to the exposed~tacky surface.
The admixture of particulate material and carrier particles is~prepared by lntimately~mixing by known methods carrier~par~ticles of average aiameter suitable~;for the~tacky~surface and a predetermined amount o particulate material. The admixture~can be applied to the tacky surface by use of a fiber pad dipped into the admixture and wiped over the tacky surface or by an applicator such a~s described in Sandner U.S. Patent 4,01~9,821. The "glossiness"
of the treated surface is plotted in gloss units determined by~means of a Photoelectric Glossmeter~
Model 610~ Photovolt Corp.,~1115 Broadway, New York, New York. ~By~varying~the we~ight ratios of particulate material to~carrier particles the degree of matte ; 25 on the surprint proof~can be controlled. Plarticulate material in the range~of less~than 50~ by weight;in the admixture provide the highe~st degree of matte (lowest amount~of gloss).~ By~ut1lizing proyressively less particulate materiaI in the admixture with the carrier particles,~an operator can modify the tacky surface to any degree of matte that is desired.
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The carrier particles are generally transparent or translucent, iner~, i.e., nonelectroscopic, spheroidal-shaped solid polymer particles with an average diameter of from about 10 S to 100~. The particle size can be measured, for example, by a Coulter Counter~ Coulter Electronics, Inc., Hialeah, Florida. The selection of the size of the carrier particles is determined by certain factors. For example, the carrier particles must be large enough to be readily removed from the tacky surface to which they are applied. Conversely, the carrier particles must be small enough so that, together with attached particulate material, the inert carrier particles can be uniformly wiped over the tacky surface. Useful carrier particles include:
polyme~hylmethacrylate, polyethylmethacrylate, polyethylene, polyvinyl chloxide, polyvinyl acetate, polystyrene, polyvinyl alcohol, cellulose acetate, and preferably ionic copolymer of ~-olefins having the ~ormula R-CH=CH2 where R is a radical selected from the class consistlng of hydrogen, alkyl of 1 to 8 carbon atoms and ~ ethylenically unsatura~ed carboxylic acid having from 3 to 8 carbon atoms, the copolymers having Erom 10% to 90~ of the carboxylic acid groups ionized by neutralization with metal ions uniformly distributed throughout the copolymer.
Admixed with the carrier particles are particulate materials haviny an average diameter oE
from 1~ to 20~, the ratio of the average diameter of the carrier particles to that of the particulate material being greater than 2 to 1. The size o~
these particles can also be measured by a Coulter Counter. A useful range of average diameter carrier particles to particulate material is between 2:1 to 3S 30:1. The amount by weight of particulate material f ~
: , in the admixture is also important. The weight ratio;
of particulate material to carrier partlcles i9 less~
than 1:1. A percent range is between about O.l~to 50~ by weight part;iculate material to 50 to 99.9~ by weight carrier~particles. As the ratio o~ ~ ~
particulate materi~al to~carrier particles changes~, the degree;o~ matte is altered as noted below.
Useful substantially colorless~particulate materia;ls~, alone or~in comblnation, Lnc~lude:~ ~cellulose acetate,~
- 10 polyvinyl alcohol, polyethy~lene~resins, waxes, ;~
diatomaaeous~silica, starches,~e.g., rice and corn; ;
; talc, etc.,~ and~co1cred plgments~or toners such~as~
; those de~s~eribed~in~the~aforementioned U.S. Pate~nts~
3,620,726;~3,909,~282~and~4,304,~43;,~in~combination~
with the substantially~colorless particulate material~s~. ~The~plgments~can be present;in an amount 0 to 20~by~wei~ght based~on~the weight o~
admixture to ~tint or~color~the taaky surface. Whi~e,~
surprising1y, the particulate mate~rial and ca~rier;
particles can~ke similar in composition, the ràt~io~s~
o avera~gè diameter~and~weight set ~orth above~mus~t ~,~ be observed.
n Charles~and~;Heiart~ U.S. Patent 4,~3~34;,00~9,~ ;
issued 198~2~June 08~ enti~tled~"Process~ or Mod~ifyi`ng~
Tacky Surfac~es~", there is~ described the appli~at~ion to ~ tacky surfaces of an admixture~of~pa~rticulate~materlal~
;~ and carrier~part~icles,~ the ratio in~the mix~u`re~of~
; the average~par`ticle dlameter tc carr;ier particles to ;~
that of the~pa~rticulate~material in the mixture~being~
greater than ~2 and the weight ratio of particulate ;
material tc~c~arrier~partioles being less~than ;l.
Among the tacky sur aces mod~ified is a tacky ~;l photosensitive layer on a negative-working multicolor :
~ 35 :
::: :
~' : , ~ -,~
~:~s~
surprint proof. In the instant process it has been found advan~ageous to expose the tacky surface, i.e., a positive-working photohardenable layer, generally through a removable protective sheet, through a superimposed screen tint, followed by removaL of the protective sheet, when present, and then applying the admixture of particulate material and carrier particles thereto. Excess particulate material and the carrier particles are then removed by procedures known to those skilled in the art. Subsequently the exposed surface may be nonimage~ise exposed to actinic radiation to further harden the surface. The exposure can be by various sources rich in ultraviolet radiation known to those skilled in the art, e.g., Berkey-Ascor Vacuum Printer, mercury vapor lamps, pulsed xenon lamps, etc., generally for a period of 10 seconds or more.
Screen tints which can be used to control exposure of the tacky surface are those which have a 20- tint value (positive percent dot area) of 25 to 75 percent with a ruling corresponding to 85 lines to ; 400 lines per inch ( 33046 to 157.5 lines per om), preferably 225 to 32S ~ines per inch ( 88.58 to 127.95 lines per cm). Preferred screen tints are those with a random photographic pattern, referred to in ~he trade as a "grained" or "mezzotint". Also useful are standard ruled tints (halftone screen tints).
~est Mode for Carr ~n~Out the Invention The best mode is illustrated in Example 1.
Industrial Applicability The process of this invention is useful in preparing improved negative-working multicolor surprint proofs having a positive-working 35 photohardenable protective layer thereon. The tacky treated surface, which is exposed through a screen tint and partic~late material/carrier particles mixture applied thereto, has a matte finish, the degree of which can be controlled by the procQss.
The matte surface is durable and nonblocking and is 5 capable of being written on by writing devices such as pencil, pen and crayon. In addition, the resistance to cracking or crazing o~ t'ne surprint proof is surprisingly lengthened. This is particularly important since surprint proofs are 10 normally retained for extended periods of time, eOg.,
OF SURPRINT PROOF
Description 5Technical Field This invention relates to a process for modifying the surface oE a surprint proof. More particularly, this invention relates to a process for modifying a tacky photosensitive outer layer of a negative-working surprint proof by exposing the tacky photosensitive layer through a screen tin~ and applying an admixture of particulate material and carrier particles to the exposed layer.
Background Art . .
15Photosensitive materials used in the preparation of surprint color proofs are o~ the positive-working or negative-working types. A
negative-working process for preparing surprint proofs is described in Cohen and Fan U.S. Patent 4,174,216. Negative-working elements useful in the nega~ive-working process comprise a support, a tacky, nonphotosensitive con~iguous layer, a photohardena~le - photoadherent layer and a s~rippable cover sheet.
After imagewise exposure to actinic radiation the 25 cover sheet is peeled away together with the exposed arèas of the photoadherent layer revealing the tacky contiguous layer beneath. The photoadherent layer in the unexposed image areas remains as a resist over the complementary portions of the con~iguous layer.
30 The tacky contiguous l~yer revealed in the exposed image areas is then toned with pigment. Layers toned with different pigments can be applied in registration over one another to form multilayer surprint color proofs. A tacky photosensitive layer PD-1875 35 generally is present as the outer layer of the proof. Dependent on the thickness of the layers, the proof may exhibit a pronounced undesirable three-dimensional effect. The multilayer surprint proofs having a positive-working photosensitive outer layer upon ageing exhibit cracks or crazes ln the surface thereof.
Methods are known by which negative-working materials can be provided with matte finishes.
Sprays have been used containing delustering agents but are messy, involve hazardous, flammable sprays, often do not cover the layer properly, yield a poor matte finish and the solvents may attack the image-forming layer. An advantageous process for providing a matte finish on negative-working multicolor surprint proofs is described and claimed in Cohen and Fan U.S. Patent 4 286 046 issued 1981 August 25. It was found by Cohen and Fan that by applying at least one layer of colloidal silica from a substantially aqueous dispersion and drying the layer to a dry coating weight of at least 20 mg/dm2 the three-dimensional effective is eliminated, and ;~ the surprint surface is hard and nonblocking, i.e., surfaces that are brought in conta~t therewith do not adhere. The wet methods for applying the matte finish are disadvantageous for the color proofer since a coater and the necessary solutions are .~ :
required with the inherent storage and cleanup problems. It is thereo~e desired that a method not requiring liquid or aqueous solutions be provided whereby the degree of matte of a tacky surface on a multilayer negative-working surprint proof can be effectively controlled, the three-dimensional efect be eliminated, a durable, nonblockiny surface be provided, and the cracking or crazing properties of the proof be improved.
-~ 2 '~ , ' ' ' , ' `
. ~,.. ..
~:
Disclosure of the Invention In accordance with this invention there isprovided in a process for modifying a tacky surface of a surprint multicolor proof having at least two non-planar, nonsilver halide, negative-working colored photoimaged elements sequentially honded to a support, and a photosensitive tacky layer present as the outer layer of the proof which comprises;
~1~ applying to the tacky surface an admixture of particulate material and carrier particles, the ratio in the admixture of the average;particle diameter of carrier particles to that of the particulate material in the admixture being greater than 2 and the weight ratio;of ~ ;
particulate material to carrier particles being less than 1, and (Z) removing excess particulate material and the car~ier particles ~rom the tacky surface, the improvement wherein prior to application to the tacky surface of the admixture of prticulate material and carrier particles the~photosensitive taaXy layer is exposed through a screen tint.
In practicing the process of the invention the tacky surface of the negative-working surpr~int proof that is modified and improved is a photosensi-tive tacky layer of a positive-workin~ photoharden-- able element. Tacky positive-working photoharden- -able elements (photohardenable layer between two removable films) are described, for example, in U.S.
Patent 3,649,26~. Positive-working elements ;are those wherein the photosensitive layer becomes hardened and nontacky in the exposed imaged areas and remains tacky in the unexposed areas. Generally the photohardenable layer contains at least one :
~ , ,.' : ' , ,. ~' ;-. . . .
. . - , ~ ~ - . . . .
' ~
~5~
free-radical initiated, chain-propagating, addition polymerizable compound containing at least one terminal ethylenic group, and an addition polymerization initiator activatable by actinic radiation, and optionally a compatible macromolecular organic polymeric binder. The tacky positive-wo king photohardenable element, after removal of one film, is present over the negative-working surprint proof, for example, of the type described in U.S.
Patent 4,174,216.
Negative-working surprint elements are elements wherein at least two photosensitive elements that have been imaged and colored with different colorants (nonplanar, nonsilver halide, colored, 15 photoimaged elements) are sequentially laminated or bonded to a suitable support surface, e.g., paper, film, e~c. In forming a surprint element, the cover sheet and any sheet support present in the photosensitive elements are removed. Preferred negative-working elements comprise, in order from top to bottom, (1) a ~trippable cover shee~, (2) a photoadheren~ layer comprising a material with ethylenically unsaturated or benzophenone ~ype groups, which is generally nontacky, (3) a tonable organic contiguous layer, e.g., a tacky, nonphotosensitivè elastomeric layer which is tonable by application of particulate material, and optionally (4) a sheet support. A positive-working photohardenable element, 2S described above is applied to the outermost colored photoimaged element of the surprint element.
Generally, the surprint element has over its support four imaged colored photopolymer elements, e.g., yellow, magenta, cyan, black, and an optional fifth nonimaged photopolymer element. Colorants and toners used in preparing the surprints are described in U.S. Patents 3,620,726, 3,909,282 and 4,304,843.
Ater the negative-working multicolor surprint proof with the positive-working photohardenable element present thereon is prepared, the surprint proof is exposed through a screen tint as described more fully below, the protective film of ` the exposed positive-workiny e}ement is removed and an aclmixture of particulate material and carrier particles~ lS applied to the exposed~tacky surface.
The admixture of particulate material and carrier particles is~prepared by lntimately~mixing by known methods carrier~par~ticles of average aiameter suitable~;for the~tacky~surface and a predetermined amount o particulate material. The admixture~can be applied to the tacky surface by use of a fiber pad dipped into the admixture and wiped over the tacky surface or by an applicator such a~s described in Sandner U.S. Patent 4,01~9,821. The "glossiness"
of the treated surface is plotted in gloss units determined by~means of a Photoelectric Glossmeter~
Model 610~ Photovolt Corp.,~1115 Broadway, New York, New York. ~By~varying~the we~ight ratios of particulate material to~carrier particles the degree of matte ; 25 on the surprint proof~can be controlled. Plarticulate material in the range~of less~than 50~ by weight;in the admixture provide the highe~st degree of matte (lowest amount~of gloss).~ By~ut1lizing proyressively less particulate materiaI in the admixture with the carrier particles,~an operator can modify the tacky surface to any degree of matte that is desired.
~, :
X
.
, ~' ', " ' ~' ' ' - ' ',, :
The carrier particles are generally transparent or translucent, iner~, i.e., nonelectroscopic, spheroidal-shaped solid polymer particles with an average diameter of from about 10 S to 100~. The particle size can be measured, for example, by a Coulter Counter~ Coulter Electronics, Inc., Hialeah, Florida. The selection of the size of the carrier particles is determined by certain factors. For example, the carrier particles must be large enough to be readily removed from the tacky surface to which they are applied. Conversely, the carrier particles must be small enough so that, together with attached particulate material, the inert carrier particles can be uniformly wiped over the tacky surface. Useful carrier particles include:
polyme~hylmethacrylate, polyethylmethacrylate, polyethylene, polyvinyl chloxide, polyvinyl acetate, polystyrene, polyvinyl alcohol, cellulose acetate, and preferably ionic copolymer of ~-olefins having the ~ormula R-CH=CH2 where R is a radical selected from the class consistlng of hydrogen, alkyl of 1 to 8 carbon atoms and ~ ethylenically unsatura~ed carboxylic acid having from 3 to 8 carbon atoms, the copolymers having Erom 10% to 90~ of the carboxylic acid groups ionized by neutralization with metal ions uniformly distributed throughout the copolymer.
Admixed with the carrier particles are particulate materials haviny an average diameter oE
from 1~ to 20~, the ratio of the average diameter of the carrier particles to that of the particulate material being greater than 2 to 1. The size o~
these particles can also be measured by a Coulter Counter. A useful range of average diameter carrier particles to particulate material is between 2:1 to 3S 30:1. The amount by weight of particulate material f ~
: , in the admixture is also important. The weight ratio;
of particulate material to carrier partlcles i9 less~
than 1:1. A percent range is between about O.l~to 50~ by weight part;iculate material to 50 to 99.9~ by weight carrier~particles. As the ratio o~ ~ ~
particulate materi~al to~carrier particles changes~, the degree;o~ matte is altered as noted below.
Useful substantially colorless~particulate materia;ls~, alone or~in comblnation, Lnc~lude:~ ~cellulose acetate,~
- 10 polyvinyl alcohol, polyethy~lene~resins, waxes, ;~
diatomaaeous~silica, starches,~e.g., rice and corn; ;
; talc, etc.,~ and~co1cred plgments~or toners such~as~
; those de~s~eribed~in~the~aforementioned U.S. Pate~nts~
3,620,726;~3,909,~282~and~4,304,~43;,~in~combination~
with the substantially~colorless particulate material~s~. ~The~plgments~can be present;in an amount 0 to 20~by~wei~ght based~on~the weight o~
admixture to ~tint or~color~the taaky surface. Whi~e,~
surprising1y, the particulate mate~rial and ca~rier;
particles can~ke similar in composition, the ràt~io~s~
o avera~gè diameter~and~weight set ~orth above~mus~t ~,~ be observed.
n Charles~and~;Heiart~ U.S. Patent 4,~3~34;,00~9,~ ;
issued 198~2~June 08~ enti~tled~"Process~ or Mod~ifyi`ng~
Tacky Surfac~es~", there is~ described the appli~at~ion to ~ tacky surfaces of an admixture~of~pa~rticulate~materlal~
;~ and carrier~part~icles,~ the ratio in~the mix~u`re~of~
; the average~par`ticle dlameter tc carr;ier particles to ;~
that of the~pa~rticulate~material in the mixture~being~
greater than ~2 and the weight ratio of particulate ;
material tc~c~arrier~partioles being less~than ;l.
Among the tacky sur aces mod~ified is a tacky ~;l photosensitive layer on a negative-working multicolor :
~ 35 :
::: :
~' : , ~ -,~
~:~s~
surprint proof. In the instant process it has been found advan~ageous to expose the tacky surface, i.e., a positive-working photohardenable layer, generally through a removable protective sheet, through a superimposed screen tint, followed by removaL of the protective sheet, when present, and then applying the admixture of particulate material and carrier particles thereto. Excess particulate material and the carrier particles are then removed by procedures known to those skilled in the art. Subsequently the exposed surface may be nonimage~ise exposed to actinic radiation to further harden the surface. The exposure can be by various sources rich in ultraviolet radiation known to those skilled in the art, e.g., Berkey-Ascor Vacuum Printer, mercury vapor lamps, pulsed xenon lamps, etc., generally for a period of 10 seconds or more.
Screen tints which can be used to control exposure of the tacky surface are those which have a 20- tint value (positive percent dot area) of 25 to 75 percent with a ruling corresponding to 85 lines to ; 400 lines per inch ( 33046 to 157.5 lines per om), preferably 225 to 32S ~ines per inch ( 88.58 to 127.95 lines per cm). Preferred screen tints are those with a random photographic pattern, referred to in ~he trade as a "grained" or "mezzotint". Also useful are standard ruled tints (halftone screen tints).
~est Mode for Carr ~n~Out the Invention The best mode is illustrated in Example 1.
Industrial Applicability The process of this invention is useful in preparing improved negative-working multicolor surprint proofs having a positive-working 35 photohardenable protective layer thereon. The tacky treated surface, which is exposed through a screen tint and partic~late material/carrier particles mixture applied thereto, has a matte finish, the degree of which can be controlled by the procQss.
The matte surface is durable and nonblocking and is 5 capable of being written on by writing devices such as pencil, pen and crayon. In addition, the resistance to cracking or crazing o~ t'ne surprint proof is surprisingly lengthened. This is particularly important since surprint proofs are 10 normally retained for extended periods of time, eOg.,
2 to 3 months and longer. Without the exposure through the screen tint untreated proofs have been known to crack and craze within 2 to 3 weeks. The multilayer surprint proof is free from the 15 three-dimensional effect and closely simulates a press proof.
Examples The following examples illustrate the invention wherein the parts and percentages are by 20 weight.
Exam~
A negative-working pre-press color proof of the surprint type is prepared as follows:
I. Nontonable Photopolymerizable Layer A coating solution of a photopolymerizable composition is prepared by mixing together the following ingredients:
Ingredient Weight (g) - Polymethyl methacrylate tMW 200,090- 41.54 300,000) Di-(3-acryloxy-2-hydroxypropyl) etner 51.86 5 of Bisphenol-A
(2-Chlorophenyl-4,5-diphenyl imidazolyl) 2.20 dimer 2-(Stilbyl-4")-(napt'no-1',2';4,5) 1,2,3- 2.20 triazol-2"-sulfonic acid phenyl estex 10 2-~ercaptobenzoxazole 1.50 Polyethylene oxide (MW 600,000) 0.70 Methanol 20.70 Methylene chloride 323.70 This solution is coated at a coating weight of about 40 mg/dm when dried on a clear polyethylene terephthalate film having a thickness of 0.0005 inch (0.0015 cm) which is surface treated by electrostatic discharge at 0.07 coulombs/ft (0.093 coulombs/m2) ~ ~I. Tonable! Tacky_Elastomer Contiguous Layer : A coating solution is prepared by mixing together the following ingredients:
~ngredient Weigh~
Random copolymer of styrene/ 19.75 butadiene (40/60) Cis-polybutadiene ~Mooney Viscosity 55-60) 79.75 Tetra-bis-[methylene 3-(3',5'-di-t- 0.50 3a butyl-4'-hydroxyphenyl) proprionate]
methane Methylene chloride to make 1333.30 This solution is coated on polyethylene terephthalate film having a releasable layer Oe polydimethyl siloxane coated thereon to give a coating weight of about 125 mg/dm2 when dried.
~ 4~
III. Laminating Procedure The supported photopolymerizable layer (I) and the supported tonable, tacky elastomer contiguous layer (II) are laminated in surface-to-surface relationship at room temperature with a pressure of about 40 psi (2.81 ks/dm2).
IV. Operations for Preparation of a Surprint The laminate (III) is further handled as follows;
The polyethylene terephthalate film with the siloxane release coating is stripped from the tonable, tacky layer and the resultiny element is then laminated at 100C to a 0.012 inch (0.03 cm) thick paper support (identified as Baryta Paper, lS marketed by the ~ntermill Corporation, Belgium). The element is then exposed to a hal~tone negative, minus-blue, color separation film record, the exposure being made through the electrostatic discharge treated, clear polyethylene terephthalate film. This exposure is about 30 seconds on an exposing device identified as a Berkey-Ascor Vacuum Printer, fitted with a photopolymer lamp (2 KW) and a Kokomo~ glass filter (No. 400) Kokomo Opalescent Glass Co., Kokomo, IN. The distance between the lamp and the vacuum frame of this device is about 38 inches (96.52 cm). After the exposure is made, the exposed element is taped securely to a suitable flat surface, and the clear polyethylene terephthalate ~ilm cover sheet is stripped by pulling at one corner with an even, continuous motion at an angle of about 135-180. The resulting exposed, photopolymerized image photoadheres to the electrostatic discharge treated film and is removed with the film thus exposing equivalent areas of the tacky, elastomer contiguous layer on the paper support. The bared areas o~ the contiguous layer are ~oned using a yellow toner, Dalamar~ Yellow (Pigment Yellow 74, C.I. No. 11741) prepared according to Example 9 of Manger et al. U.S. Patent 4,215,193. A second 5 lamlnate (III) having its polyethylene terephthalate film with release coating removed as described above is laminated to the surface of the yellow image and is exposed to a halftone, negative, minus-green color separation-film record in registration. The clear, 10 surface treated polyethylene terephthalate film of the second laminate is stripped from the contiguous layer leaving bared an image which is toned with a magenta toner, a dispersion consisting of 50 percent mixture of quinacridone ma~enta, Quindo Magenta ~C.I. Pigment Red 122) and Indo Brilliant Scarle~t toner lPigment Red 123, C.I. ~71145) and 50 percent cellulose acetate, prepared as described in Example 11 of U~S. Patent 4,215,193. The process is then repeated for the minus-red, (phthalocyanine cyan 2Q toner, a dispersion of 50 percent mixture of Monastral~ ~lue G (Copper Phthalocyanine Pigment Blue ; 15, C.I. #74260) and 50 percent cellulose acetate prepared as described in Example 1 of U.S. Patent 4,215,193), and black, Carbon Black, Sterling NS N774 ~C. I. Pigment Black 7, C.I. ~77266 prepared as described in Example 10 of U.S. Patent 4,215,193), negative records. This procedure yielZs a four-color negative surprin~ proof. Onto the outer surface of the four-color proof is laminated at 110C a positive-working photopolymer element of a 0.0003 inch (0.008 mm) layer and a 0.001 inch (0.025 mm) thick polyethylene terephthalate support. The photopolymer layer is prepared by mixing together the following ingredients:
In~redient Amount (parts) Polymethylmethacrylate, molecular weight 30,000, density 1.13 g/cc 32.40 5 Trimethylolpropane trimethacrylate 35.60 2-o-Chlorophenyl-4,5-bis-~m-methoxy-phenyl) imidaæolyl dimer 1.58 2-Mercaptobenzothiazole 0.79 10 Polyoxyethylene lauryl ether7.90 The mixture is dissolved in methylene chloride ~20%
solution) and is coated onto a 0.001 inch (.0025 cm) thick polyethylene terephthalate support.
The four-color surprint proof having the 15 positive-working photopolymer element thereon is returned to the exposure device described above.
Over the positive-working photopolymer element is placed a screen tint ~mezzotint) with a 55 positive percent dot area derived from a Policrom~ GKKK
Neutral Grey Fine Grain Screen manufactured by Policrom Photo Products S.p.A. Bergamo, Italy.
Vacuum is applied for about one minute and the element is exposed for about 15 seconds (dot for dot rendition~. The exposed element is removed from the vacuum frame, and the polyethylene terephthalate support is removed. An admixture of particulate cellulose aceta~e (4 g, about 5~ average diameter) and Surlyn~A ionomer resin beads (carrier particles~
manufactured by E. I. du Pont de Nemours and Company, Wilmington, Delaware (16 g, about 2;~ average diameter) is applied to the exposed pho~opolymer surface by means of a fiber pad dipped into the admixture. The surface is wiped with a cotton cloth to remove excess cellulose acetate and all the carrier par~icles. The four-color proof has a uniform matte finish which is clean, dry and resembles a press sheet. The finish is durable, is nonblocking, and is capable of being written on with pencil, pen or crayon. The ~repared prooÇs show no deterioration due to crac~ing or crazing for a period of at least three months at ambient temperature.
Example 2 Example l is repeated except that in place of the 55 positive percent dot area screen tint is used a 25 positive percent dot area screen tint derived from a similar screen as described in Example l. The resultant proof exhibits the same desirable features with a lesser degree of matte.
Exam~e 3 Example 1 is repeated except that the positive-working photopolymer element with the screen tint in place is exposed for 30 seconds in the exposure device described in Example l. The resultant proof exhibits the same desirable features 20 wi~h a lesser degree of matte.
Examples The following examples illustrate the invention wherein the parts and percentages are by 20 weight.
Exam~
A negative-working pre-press color proof of the surprint type is prepared as follows:
I. Nontonable Photopolymerizable Layer A coating solution of a photopolymerizable composition is prepared by mixing together the following ingredients:
Ingredient Weight (g) - Polymethyl methacrylate tMW 200,090- 41.54 300,000) Di-(3-acryloxy-2-hydroxypropyl) etner 51.86 5 of Bisphenol-A
(2-Chlorophenyl-4,5-diphenyl imidazolyl) 2.20 dimer 2-(Stilbyl-4")-(napt'no-1',2';4,5) 1,2,3- 2.20 triazol-2"-sulfonic acid phenyl estex 10 2-~ercaptobenzoxazole 1.50 Polyethylene oxide (MW 600,000) 0.70 Methanol 20.70 Methylene chloride 323.70 This solution is coated at a coating weight of about 40 mg/dm when dried on a clear polyethylene terephthalate film having a thickness of 0.0005 inch (0.0015 cm) which is surface treated by electrostatic discharge at 0.07 coulombs/ft (0.093 coulombs/m2) ~ ~I. Tonable! Tacky_Elastomer Contiguous Layer : A coating solution is prepared by mixing together the following ingredients:
~ngredient Weigh~
Random copolymer of styrene/ 19.75 butadiene (40/60) Cis-polybutadiene ~Mooney Viscosity 55-60) 79.75 Tetra-bis-[methylene 3-(3',5'-di-t- 0.50 3a butyl-4'-hydroxyphenyl) proprionate]
methane Methylene chloride to make 1333.30 This solution is coated on polyethylene terephthalate film having a releasable layer Oe polydimethyl siloxane coated thereon to give a coating weight of about 125 mg/dm2 when dried.
~ 4~
III. Laminating Procedure The supported photopolymerizable layer (I) and the supported tonable, tacky elastomer contiguous layer (II) are laminated in surface-to-surface relationship at room temperature with a pressure of about 40 psi (2.81 ks/dm2).
IV. Operations for Preparation of a Surprint The laminate (III) is further handled as follows;
The polyethylene terephthalate film with the siloxane release coating is stripped from the tonable, tacky layer and the resultiny element is then laminated at 100C to a 0.012 inch (0.03 cm) thick paper support (identified as Baryta Paper, lS marketed by the ~ntermill Corporation, Belgium). The element is then exposed to a hal~tone negative, minus-blue, color separation film record, the exposure being made through the electrostatic discharge treated, clear polyethylene terephthalate film. This exposure is about 30 seconds on an exposing device identified as a Berkey-Ascor Vacuum Printer, fitted with a photopolymer lamp (2 KW) and a Kokomo~ glass filter (No. 400) Kokomo Opalescent Glass Co., Kokomo, IN. The distance between the lamp and the vacuum frame of this device is about 38 inches (96.52 cm). After the exposure is made, the exposed element is taped securely to a suitable flat surface, and the clear polyethylene terephthalate ~ilm cover sheet is stripped by pulling at one corner with an even, continuous motion at an angle of about 135-180. The resulting exposed, photopolymerized image photoadheres to the electrostatic discharge treated film and is removed with the film thus exposing equivalent areas of the tacky, elastomer contiguous layer on the paper support. The bared areas o~ the contiguous layer are ~oned using a yellow toner, Dalamar~ Yellow (Pigment Yellow 74, C.I. No. 11741) prepared according to Example 9 of Manger et al. U.S. Patent 4,215,193. A second 5 lamlnate (III) having its polyethylene terephthalate film with release coating removed as described above is laminated to the surface of the yellow image and is exposed to a halftone, negative, minus-green color separation-film record in registration. The clear, 10 surface treated polyethylene terephthalate film of the second laminate is stripped from the contiguous layer leaving bared an image which is toned with a magenta toner, a dispersion consisting of 50 percent mixture of quinacridone ma~enta, Quindo Magenta ~C.I. Pigment Red 122) and Indo Brilliant Scarle~t toner lPigment Red 123, C.I. ~71145) and 50 percent cellulose acetate, prepared as described in Example 11 of U~S. Patent 4,215,193. The process is then repeated for the minus-red, (phthalocyanine cyan 2Q toner, a dispersion of 50 percent mixture of Monastral~ ~lue G (Copper Phthalocyanine Pigment Blue ; 15, C.I. #74260) and 50 percent cellulose acetate prepared as described in Example 1 of U.S. Patent 4,215,193), and black, Carbon Black, Sterling NS N774 ~C. I. Pigment Black 7, C.I. ~77266 prepared as described in Example 10 of U.S. Patent 4,215,193), negative records. This procedure yielZs a four-color negative surprin~ proof. Onto the outer surface of the four-color proof is laminated at 110C a positive-working photopolymer element of a 0.0003 inch (0.008 mm) layer and a 0.001 inch (0.025 mm) thick polyethylene terephthalate support. The photopolymer layer is prepared by mixing together the following ingredients:
In~redient Amount (parts) Polymethylmethacrylate, molecular weight 30,000, density 1.13 g/cc 32.40 5 Trimethylolpropane trimethacrylate 35.60 2-o-Chlorophenyl-4,5-bis-~m-methoxy-phenyl) imidaæolyl dimer 1.58 2-Mercaptobenzothiazole 0.79 10 Polyoxyethylene lauryl ether7.90 The mixture is dissolved in methylene chloride ~20%
solution) and is coated onto a 0.001 inch (.0025 cm) thick polyethylene terephthalate support.
The four-color surprint proof having the 15 positive-working photopolymer element thereon is returned to the exposure device described above.
Over the positive-working photopolymer element is placed a screen tint ~mezzotint) with a 55 positive percent dot area derived from a Policrom~ GKKK
Neutral Grey Fine Grain Screen manufactured by Policrom Photo Products S.p.A. Bergamo, Italy.
Vacuum is applied for about one minute and the element is exposed for about 15 seconds (dot for dot rendition~. The exposed element is removed from the vacuum frame, and the polyethylene terephthalate support is removed. An admixture of particulate cellulose aceta~e (4 g, about 5~ average diameter) and Surlyn~A ionomer resin beads (carrier particles~
manufactured by E. I. du Pont de Nemours and Company, Wilmington, Delaware (16 g, about 2;~ average diameter) is applied to the exposed pho~opolymer surface by means of a fiber pad dipped into the admixture. The surface is wiped with a cotton cloth to remove excess cellulose acetate and all the carrier par~icles. The four-color proof has a uniform matte finish which is clean, dry and resembles a press sheet. The finish is durable, is nonblocking, and is capable of being written on with pencil, pen or crayon. The ~repared prooÇs show no deterioration due to crac~ing or crazing for a period of at least three months at ambient temperature.
Example 2 Example l is repeated except that in place of the 55 positive percent dot area screen tint is used a 25 positive percent dot area screen tint derived from a similar screen as described in Example l. The resultant proof exhibits the same desirable features with a lesser degree of matte.
Exam~e 3 Example 1 is repeated except that the positive-working photopolymer element with the screen tint in place is exposed for 30 seconds in the exposure device described in Example l. The resultant proof exhibits the same desirable features 20 wi~h a lesser degree of matte.
Claims (11)
1. In a process for modifying a tacky sur-face of a surprint multicolor proof having at least two nonplanar, nonsilver halide, negative-working colored photoimaged elements sequentially bonded to a support, and a photosensitive tacky layer present as the outer layer of the proof which comprises (1) applying to the tacky surface an admixture of particulate material and carrier particles, the ratio in the admixture of the average particle diameter of carrier particles to that of the particulate material in the ad-mixture being greater than 2 and the weight ratio of particulate material to carrier particles being less than 1, and (2) removing excess particulate material and the carrier particles from the tacky surface, the improvement wherein prior to application to the tacky surface of the admixture of particulate material and carrier particles the photosensitive tacky layer is exposed through a screen tint.
2. A process according to Claim 1 wherein the tacky layer is a photohardenable layer containing at least one free-radical initiated, chain propagating, addition polymerizable compound containing at least one terminal ethylenic group, and an addition poly-merization initiator activatable by actinie radiation, and, optionally a compatible macromolecular organic polymeric binder.
3. A process according to Claim 1 or Claim 2 wherein a protective sheet is present on the tacky layer during the exposure, the protective sheet being removed prior to application of the admixture of particulate material and carrier particles.
4. A process according to Claim 1 wherein the particulate material is cellulose acetate.
5. A process according to Claim 1 wherein the carrier particles are an ionic copolymer.
6. A process according to Claim 1 wherein the admixture of the particulate material and carrier particles contains particulate pigment material.
7. A process according to Claim 1 wherein the negative-working photoimaged elements, prior to exposure, comprise a photoadherent layer comprising a nontacky photohardenable material with ethylenically unsaturated or benzophenone type groups, and a contiguous layer of a nonphotosensitive, tacky organic material.
8. A process according to Claim 7 wherein each colored photoimaged element has been exposed through a different color separation negative and the respective photoadherent layers have been colored in a spectral region corresponding to the color separation negative used for the exposure.
9. A process according to Claim 8 wherein four negative-working photoimaged elements are present in the surprint multicolor proof, and the elements and colored separation negatives correspond, respectively, to yellow, magenta, cyan and black.
10. A process according to Claim 1 wherein the screen tint is a halftone screen tint having a tint value of 25 to 75 percent with a screen ruling of 85 to 400 lines per inch.
11. A process according to Claim 1 wherein the screen tint has a tint value of 25 to 75 percent with a random pattern corresponding to 85 to 400 lines per inch.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US189,828 | 1980-09-23 | ||
| US06/189,828 US4321320A (en) | 1980-09-23 | 1980-09-23 | Process for surface improvement of surprint proof involves exposure thru halftone screen tint |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1154291A true CA1154291A (en) | 1983-09-27 |
Family
ID=22698938
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000386426A Expired CA1154291A (en) | 1980-09-23 | 1981-09-22 | Modifying a surprint proof having a photosensitive tacky layer by exposure through a screen tint |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US4321320A (en) |
| JP (1) | JPS5785054A (en) |
| CA (1) | CA1154291A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4427761A (en) | 1982-12-02 | 1984-01-24 | E. I. Du Pont De Nemours And Company | Process for surface improvement of surprint proof with transparentized particulate material |
| US4634658A (en) * | 1984-12-27 | 1987-01-06 | E. I. Du Pont De Nemours And Company | Process for preparing surprint proof of an improved support |
| JPH0734110B2 (en) * | 1985-07-12 | 1995-04-12 | 富士写真フイルム株式会社 | Image density changing method in simple color proof |
| US5001037A (en) * | 1990-02-05 | 1991-03-19 | E. I. Du Pont De Nemours And Company | Method of making overlay proofs comprising precolored and toned images |
| US5122437A (en) * | 1990-02-05 | 1992-06-16 | E. I. Du Pont De Nemours And Company | Overlay proofs comprising precolored and toned images |
| US6123877A (en) * | 1994-12-28 | 2000-09-26 | Nashua Corporation | Asymmetric light diffusing material |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US45245A (en) * | 1864-11-29 | Elevator | ||
| US4247619A (en) * | 1979-12-20 | 1981-01-27 | E. I. Du Pont De Nemours And Company | Negative-working multilayer photosensitive tonable element |
| US4229518A (en) * | 1976-07-08 | 1980-10-21 | E. I. Du Pont De Nemours And Company | Photohardenable elements with a non-tacky matte finish |
-
1980
- 1980-09-23 US US06/189,828 patent/US4321320A/en not_active Expired - Lifetime
-
1981
- 1981-09-22 CA CA000386426A patent/CA1154291A/en not_active Expired
- 1981-09-22 JP JP56148941A patent/JPS5785054A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| US4321320A (en) | 1982-03-23 |
| JPS6348048B2 (en) | 1988-09-27 |
| JPS5785054A (en) | 1982-05-27 |
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