US2169003A - Photosensitive material - Google Patents

Photosensitive material Download PDF

Info

Publication number
US2169003A
US2169003A US132081A US13208137A US2169003A US 2169003 A US2169003 A US 2169003A US 132081 A US132081 A US 132081A US 13208137 A US13208137 A US 13208137A US 2169003 A US2169003 A US 2169003A
Authority
US
United States
Prior art keywords
exposure
light
color
resist
change
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 - Lifetime
Application number
US132081A
Inventor
Murray Alexander
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Eastman Kodak Co
Original Assignee
Eastman Kodak Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US132081A priority Critical patent/US2169003A/en
Priority claimed from GB861838A external-priority patent/GB512914A/en
Application granted granted Critical
Publication of US2169003A publication Critical patent/US2169003A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03FPHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004Photosensitive materials
    • G03F7/09Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

Definitions

  • This invention relates to photo-sensitive materials and particularly to photo-sensitive photographic materials of the developing out type.
  • One particular embodiment of. the invention relates to photo-sensitive resists of the type employed by the graphic arts in the manufacture of printing plates.
  • the general object of the invention is to produce a photo-sensitive material which, under exposure to light, visibly changes by an .amount definitely indicative of the exposure to which it has been subjected whereby the correct exposure for getting a useful image when the material has been developed in a suitable way, is
  • this visible change is a change in color hue rather than merely a change in color saturation.
  • the object of the invention is to provide a photographic developing-out material which is capable of acting as its own actinometer.
  • the image obtained when a developing-out photographic material is processed is satisfactory only when the exposure to which the material was subjected is within a certain range (i. e. not underexposed or overexposed).
  • a photographic material made according to the invention is subjected to sufficient exposure to give a predetermined amount of change in its appearance and is then developed in a. suitable manner giving a satisfactory image.
  • the invention is particularly useful with materials requiring relatively long exposure to light of a certain intensity. In this case, the exposure is started and allowed to continue until the predetermined amount of change in appearance is obtained. The material is then ready to be developed, and when developed will give a satisfactory image.
  • one method of making printing plates comprises coating a resist on an etchable base (preferably metal) exposing the plate through a half-tone negative, processing the plate in a suitable manit) ner to differentially remove the resist according to the exposure received and then etching the exposed portions of the base.
  • an etchable base preferably metal
  • a water insoluble photomechanical resist free from metals such as those based on certain types of light sensitive organic compounds (e. g. dici'nnamyl acetone).
  • the accompanying chart refers particularly to the use of dicinnamyl acetone.
  • This substance is yellow, and when given sufllcient exposure to make a developable print, the yellow color is partly or wholly bleached. This color change in itself is insuflicient to be useful in estimating the exposure since it is dimcult, if not impossible, to accurately judge the relative densities of light yellows.
  • the effect of exposing a resist comprising dicinnamyl acetone is indicated by the arrows I and 2.
  • the correct exposure as shown on the chart is that obtained when the exposure is sufficient to bleach the yellow to a certain density of light yellow.
  • a violet dye is incorporated. in the resist which together with the yellow color of the dicinnamyl acetone gives agreenish coating. This step is indicated by the arrows I and l on the chart.
  • a suitable resist is as follows: dicinnamyl acetone, 4 grams; pale Kauri resin, 6 grams; ethyl methyl ketone, grams; toluene, 30 grams; benzyl alcohol, 1 gram. To this is added 0.2 gram crystal violet base.
  • the violet dye chosen for this purpose should, of course, be compatible with the processes to which the resist is to be subjected and preferably should be stable under the action of light. How- .is provided for the first time a photo-sensitive resist whose coloring material changes under the action of light by an amount sufficient to be useful as an actinometer.
  • the invention may be applied equally well to other types of photographic materials, but as pointed out above, it is particularly suitable for use with photo-sensitive resists.
  • a photomechanical resist comprising dicinnamyl acetone and a violet dye substantially stable under exposure to any light and compatible with the processes for which the resist is intended, the proportion of violet dye to dicinnamyl acetone being such that the unexposed resist has a hue in the spectrum region of green and blue.
  • a photomechanical resist comprising dicinnamyl acetone and a dye of the triphenylmethane violet bases, in such proportion that the resist shifts in hue from green to shorter wavelengths with exposure to light.
  • a photo sensitive layer comprising a colored light sensitive material whose color saturation changes with exposure to substantially any light to which said material is sensitive and a dye substantially stable to any light and of a contrasting color such that the change in color saturation appears as a change in hue, the relative proportion of the dye to the substance whose color saturation changes being such that the unexposed material has a hue in a spectrum region very different from that of the dye alone.
  • a photosensitive layer comprising a light sensitive material having a color which changes with exposure to light and a dye substantially stable under exposure to any light and of a different color whereby the apparent change in color is enhanced, the relative proportion of the dye in the layer being such that the unexposed material has a hue different from that of the dye alone.

Description

Aug. 8, 1939. A. MURRAY PHOTOSENSITIVE MATERIAL VIOLET DYE ' Filed larch 20, 1937 LIGHT-P" com-er I IL EXPOSURE YELLOW Alexander Murray INVENTOR M Q.JLMZM ATTORNEYS Patented Aug. 8, 1939 UNITED STATES PATENT OFFICE PHOTOSENSITIVE MATERIAL Application March 20, 1937, Serial No. 132,081
4 Claims.
This invention relates to photo-sensitive materials and particularly to photo-sensitive photographic materials of the developing out type. One particular embodiment of. the invention relates to photo-sensitive resists of the type employed by the graphic arts in the manufacture of printing plates.
The general object of the invention is to produce a photo-sensitive material which, under exposure to light, visibly changes by an .amount definitely indicative of the exposure to which it has been subjected whereby the correct exposure for getting a useful image when the material has been developed in a suitable way, is
' obtained when the exposure is sufllcient to give a predetermined amount of said visible change. In the preferable embodiment of the invention, this visible change is a change in color hue rather than merely a change in color saturation.
It is a particular object of the invention to provide a photo-mechanical resist having the above-described properties.
It is a special object of the invention, when using photo-mechanical resists such as dicinnamyl acetone, whose color changes slightly under exposure to light, toenhance the apparent color change sufliciently to be useful as a measure of exposure.
Thus the object of the invention is to provide a photographic developing-out material which is capable of acting as its own actinometer.
As is well known to those skilled in the art, the image obtained when a developing-out photographic material is processed, is satisfactory only when the exposure to which the material was subjected is within a certain range (i. e. not underexposed or overexposed). A photographic material made according to the invention, is subjected to sufficient exposure to give a predetermined amount of change in its appearance and is then developed in a. suitable manner giving a satisfactory image. The invention is particularly useful with materials requiring relatively long exposure to light of a certain intensity. In this case, the exposure is started and allowed to continue until the predetermined amount of change in appearance is obtained. The material is then ready to be developed, and when developed will give a satisfactory image.
Other objects and advantages of the invention will become apparent from the following description when read in connection with the accompanying drawing which shows, by means of a flow chart, the results obtained when using one specific embodiment of the invention.
The following description relates only to this specific but very useful embodiment of the invention. I v '5 As is well known in the graphic arts, one method of making printing plates comprises coating a resist on an etchable base (preferably metal) exposing the plate through a half-tone negative, processing the plate in a suitable manit) ner to differentially remove the resist according to the exposure received and then etching the exposed portions of the base.
Many photo-mechanical sensitizers exhibit a color change with exposure, but to a degree 15 which is so slight as to be valueless in judging the course of exposure. For example, the bichromated colloids develop a pale brownishyellow image, well known to those skilled in the art, which is not visible through the negative m during exposure and is of very little assistance to the judgment of the operator after exposure. As is well known in trade practice, prints are frequently remade because the printer has misjudged the density of the negative or has been unable to estimate correctly the retarding eflfect of stain or 108.
For many purposes it is desirable to use a water insoluble photomechanical resist free from metals such as those based on certain types of light sensitive organic compounds (e. g. dici'nnamyl acetone). The accompanying chart refers particularly to the use of dicinnamyl acetone. This substance is yellow, and when given sufllcient exposure to make a developable print, the yellow color is partly or wholly bleached. This color change in itself is insuflicient to be useful in estimating the exposure since it is dimcult, if not impossible, to accurately judge the relative densities of light yellows.
0n the chart, the effect of exposing a resist comprising dicinnamyl acetone is indicated by the arrows I and 2. The correct exposure as shown on the chart is that obtained when the exposure is sufficient to bleach the yellow to a certain density of light yellow.
In accordance with the invention a violet dye is incorporated. in the resist which together with the yellow color of the dicinnamyl acetone gives agreenish coating. This step is indicated by the arrows I and l on the chart.
When this green coating is exposed to light, the yellow component fades in proportion to the exposure and the exposedregion becomes blue and then a bright blue-violet as indicated by the arrows l, and 5. This change produces a high visible contrast with the.background color in which the color saturation is much lower and the hue entirely different. Actually, this color change can be easily seen through the clear parts of the negative with which it is in contact during exposure and is an accurate indication of the correct exposure. This advantage is, of course, due to the fact that the human eye is more sensitive to changes from green to blue than in changes from yellow to light yellow.
I have found that various dyes are suitable, for example, the bases of the triphenylmethane violets, such as methyl violet base, crystal violet base, and ethyl violet base. Certain solutions, useful as resists and containing dicinnamyl acetone, keep almost indefinitely. I have found that it is desirable to add a small amount of crystal violet base to such a solution just before coating the plates, at least within 24 hours prior to such coating. A suitable resist is as follows: dicinnamyl acetone, 4 grams; pale Kauri resin, 6 grams; ethyl methyl ketone, grams; toluene, 30 grams; benzyl alcohol, 1 gram. To this is added 0.2 gram crystal violet base. When the liquid is first applied to the metal, it is almost colorless, but as it dries, it develops the blue-green color which was discussed in detail above. The coated metal plate after drying, will keep for a considerable time.
The violet dye chosen for this purpose should, of course, be compatible with the processes to which the resist is to be subjected and preferably should be stable under the action of light. How- .is provided for the first time a photo-sensitive resist whose coloring material changes under the action of light by an amount sufficient to be useful as an actinometer.
The invention may be applied equally well to other types of photographic materials, but as pointed out above, it is particularly suitable for use with photo-sensitive resists.
Having thus described one embodiment of my invention, I wish to point out that it is not limited to the specific materials employed but is of the scope of the appended claims.
What I claim and wish to protect by Letters Patent of the United States is:
1. A photomechanical resist comprising dicinnamyl acetone and a violet dye substantially stable under exposure to any light and compatible with the processes for which the resist is intended, the proportion of violet dye to dicinnamyl acetone being such that the unexposed resist has a hue in the spectrum region of green and blue.
2. A photomechanical resist comprising dicinnamyl acetone and a dye of the triphenylmethane violet bases, in such proportion that the resist shifts in hue from green to shorter wavelengths with exposure to light.
3. A photo sensitive layer comprising a colored light sensitive material whose color saturation changes with exposure to substantially any light to which said material is sensitive and a dye substantially stable to any light and of a contrasting color such that the change in color saturation appears as a change in hue, the relative proportion of the dye to the substance whose color saturation changes being such that the unexposed material has a hue in a spectrum region very different from that of the dye alone.
4. A photosensitive layer comprising a light sensitive material having a color which changes with exposure to light and a dye substantially stable under exposure to any light and of a different color whereby the apparent change in color is enhanced, the relative proportion of the dye in the layer being such that the unexposed material has a hue different from that of the dye alone.
ALEXANDER MURRAY.
US132081A 1937-03-20 1937-03-20 Photosensitive material Expired - Lifetime US2169003A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US132081A US2169003A (en) 1937-03-20 1937-03-20 Photosensitive material

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US132081A US2169003A (en) 1937-03-20 1937-03-20 Photosensitive material
GB861838A GB512914A (en) 1938-03-21 1938-03-21 Improved photo-mechanical resist

Publications (1)

Publication Number Publication Date
US2169003A true US2169003A (en) 1939-08-08

Family

ID=26242296

Family Applications (1)

Application Number Title Priority Date Filing Date
US132081A Expired - Lifetime US2169003A (en) 1937-03-20 1937-03-20 Photosensitive material

Country Status (1)

Country Link
US (1) US2169003A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2678883A (en) * 1948-12-31 1954-05-18 Eastman Kodak Co Preparation of photographic emulsions
US2686122A (en) * 1947-03-07 1954-08-10 Harold C Purdy Photographic light-sensitive element
US2773767A (en) * 1951-04-17 1956-12-11 Azoplate Corp Light sensitive material
FR2480953A1 (en) * 1980-04-16 1981-10-23 Mecanorma Sa EQUIPMENT FOR THE REPRODUCTION OF AN IMAGE UNDER THE ACTION OF A RADIATION AND METHOD OF IMPLEMENTING SAID MATERIAL

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2686122A (en) * 1947-03-07 1954-08-10 Harold C Purdy Photographic light-sensitive element
US2678883A (en) * 1948-12-31 1954-05-18 Eastman Kodak Co Preparation of photographic emulsions
US2773767A (en) * 1951-04-17 1956-12-11 Azoplate Corp Light sensitive material
FR2480953A1 (en) * 1980-04-16 1981-10-23 Mecanorma Sa EQUIPMENT FOR THE REPRODUCTION OF AN IMAGE UNDER THE ACTION OF A RADIATION AND METHOD OF IMPLEMENTING SAID MATERIAL

Similar Documents

Publication Publication Date Title
DE2331377C2 (en) Photosensitive copying material
US2675313A (en) Photographic reproduction process
IE50312B1 (en) Improved positive-working resist materials and their use in a formation of a negative resist pattern on a substrate
GB2045967A (en) Method of producing colour filters
JPS63501606A (en) Improved photoimaging methods and compositions
US2083675A (en) Photographic print-out material having a design thereon
US2169003A (en) Photosensitive material
US4250242A (en) Uniform exposure of positive-acting diazo type materials through support
US3578451A (en) Integral negative type positive photolithographic plate
US4578341A (en) Acidic photosensitive relief image-forming materials with indicator pigment or dye
US4154613A (en) Positive-acting diazo type materials having photodecomposed gradient
JPS60238829A (en) Formation of pattern
US3582342A (en) Light-sensitive photographic materials
DE2037345A1 (en) Photosensitive copying paste
US4564581A (en) Process of preparing screen stencil using diazo photosensitive compositions with acidic p-H indicator
US3628954A (en) Diazo material and visible light development process therefore
US2687949A (en) Method and material for making overlay mask
US4296193A (en) Photosensitive positive diazo material with copolymer of acrylamide and diacetoneacrylamide and a process for developing to form color relief image
US3856528A (en) Color toned photopolymerization imaging process
US3406067A (en) Colored photoresist and method of preparation
US2785958A (en) Method for quantitatively testing for thiosulfate radical
US3052542A (en) Intermediate master for use in the diazotype process and a process for producing same
US3053658A (en) Photolithography
US1574356A (en) Light-sensitive medium and process of producing the same
US5215865A (en) Image developing method utilizing sodium sulfide and ammonium polysulfide developer solution whereby exposed copper substrate surface changes color