EP0038016B1 - Matériel vésiculaire sensible à la lumière - Google Patents

Matériel vésiculaire sensible à la lumière Download PDF

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Publication number
EP0038016B1
EP0038016B1 EP81102626A EP81102626A EP0038016B1 EP 0038016 B1 EP0038016 B1 EP 0038016B1 EP 81102626 A EP81102626 A EP 81102626A EP 81102626 A EP81102626 A EP 81102626A EP 0038016 B1 EP0038016 B1 EP 0038016B1
Authority
EP
European Patent Office
Prior art keywords
weight
copolymer
vinylidene chloride
methacrylonitrile
binder
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
Application number
EP81102626A
Other languages
German (de)
English (en)
Other versions
EP0038016A1 (fr
Inventor
Markus Dr. Seibel
Irmgard Bindrum
Bernd Dr. Huber
Dieter Bodenheimer
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.)
Hoechst AG
Original Assignee
Hoechst AG
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 Hoechst AG filed Critical Hoechst AG
Publication of EP0038016A1 publication Critical patent/EP0038016A1/fr
Application granted granted Critical
Publication of EP0038016B1 publication Critical patent/EP0038016B1/fr
Expired legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/60—Processes for obtaining vesicular 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
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/106—Binder containing
    • Y10S430/108—Polyolefin or halogen containing

Definitions

  • the invention relates to a light-sensitive recording material for the vesicular process from a layer of a binder and a light-sensitive compound applied to a suitable base.
  • Recording materials for producing vesicular images consist of a layer of a thermoplastic resin and a light-sensitive compound dispersed therein, which decomposes on exposure to gas evolution.
  • the light-sensitive layer is applied to a base.
  • the light-sensitive compounds in the layer decompose according to the original.
  • the film is heated at least to the glass transition temperature of the thermoplastic resin, which causes softening, so that the photolytically formed gas enclosed in the binder expands and forms bubbles. These bubbles reflect or refract the light, which can make an image visible under suitable optical conditions.
  • binder materials have also been known. They are aimed at combining the good properties, for example the photographic sensitivity, of polymethacrylonitrile with those of other resins.
  • the copolymers developed consist of various vinyl monomers which are copolymerizable with methacrylonitrile and are compatible with other organic film-forming materials. These vesicular materials have improved physical properties compared to methacrylitrile homopolymers, but they do not show the high degree of gas exploitation. These systems have also proven to be relatively incompatible.
  • DE-A-2 438 157 discloses mixtures of pure polymethacrylonitrile with other resins such as a vinylidene chloride-acrylonitrile copolymer. It is emphasized that, contrary to what has been known up to now, compatible mixtures with other polymers can be obtained, but this compatibility can only exist within narrow limits because complicated solvent mixtures have to be used, some of which are toxic or very environmentally unfriendly, such as tetrahydrofuran, dioxane, acetonitrile .
  • a recording material of the type mentioned at the outset which is characterized in that the recording material contains or consists of a copolymer of methacrylonitrile and vinylidene chloride which is soluble in butanone as the binder.
  • the recording material preferably contains as a binder a copolymer of methacrylonitrile and vinylidene chloride which is soluble in butanone, together with a copolymer of vinylidene chloride and acrylonitrile, that is miscible with this in butanone.
  • the binder used has good film-forming ability and good adhesion to the base.
  • the film surface shows good scratch resistance. Due to the particularly good compatibility of the components, the material shows a high level of transparency.
  • the recording material also shows very good gas utilization due to its high gas density.
  • the underlay can be transparent, opaque or opaque, colored or uncolored.
  • the base used is, for example, plastic films such as those made of polyethylene or polypropylene, preferably those made of polyethylene terephthalate.
  • the base can also consist of paper, metal foils or metal plates, glass plates or the like.
  • the documents can be provided with a substrate to improve liability.
  • the copolymer of methacrylonitrile and vinylidene chloride can be prepared by one of the known processes. For technical reasons, the polymerization is preferably carried out in solution because reprecipitation and drying are avoided.
  • the weight ratio of the constituents in the copolymer is preferably 80 to 40 parts of methacrylonitrile.
  • the copolymer has a glass transition temperature (tg) in a range from 80 ° C. to 130 ° C., the definition according to the polymer handbook by J. Brandrup and EH Immergut, 2nd edition, page 111139 ff., John Wiley Verlag, for the glass transition temperature , New York (1975).
  • the copolymer of methacrylonitrile and vinylidene chloride can be used alone as a binder. However, it is preferably used in a mixture with a vinylidene chloride-acrylonitrile copolymer which is soluble in butanone.
  • the solution of the vinylidene chloride-acrylonitrile copolymer should be miscible with the solution of the copolymer of methacrylonitrile and vinylidene chloride in any ratio.
  • the copolymer of methacrylonitrile and vinylidene chloride in a 20% solution in butanone, measured at 20 ° C. has a viscosity of less than 50 mPas, preferably between 2.5 and 30 mPas. Those having a viscosity in the range from 5 to 15 mPas are very particularly preferred.
  • the mixing ratios of the two copolymers largely depend on the properties which one wishes to impart to the recording material according to the invention. So you can use the pure methacrylonitrile-vinylidene chloride copolymer if you attach particular importance to high thermal image stability even at a low development temperature. On the other hand, by adding small amounts of the vinylidene chloride-acrylonitrile copolymer, the exposure time is shortened, which then does not change significantly with further addition. However, if the proportion of the vinylidene chloride-acrylonitrile copolymer in the binder mixture is increased too much, the thermal image stability drops below a level that is no longer acceptable for practical conditions. With regard to the thermal image stability, an approximate proportion of 60% by weight of vinylidene chloride can be given as the upper limit.
  • the layers can be hardened by more intensive drying. As a result, the development temperature required for a sufficient density is increased, depending on the degree of hardening, from 90 to 110 ° C. or above, but the thermal image stability then proves to be good even in the case of such mixtures in which they are already less than practical in the case of non-hardened layers usable level drops. With the hardened layers, the exposure time is not shortened by increasing amounts of the vinylidene chloride-acrylonitrile copolymer.
  • the amount of the photosensitive compound is not critical.
  • the amount of the diazonium salt is generally not more than 20% and preferably in a range of 1 to 20% based on the weight of the binder.
  • a mixture of 209 g of MAN and 193 g of VCl 2 is introduced into a 2-1 glass autoclave, which was first flushed with nitrogen, the latter being stabilized with 0.015 parts by weight of hydroquinone monomethyl ether, together with 1.05 azo-bis-isobutyronitrile (AIBN) and 153 g butanone.
  • AIBN azo-bis-isobutyronitrile
  • the autoclave is closed and heated to 100 ° C. with stirring.
  • the clear, yellow and viscous product contains more than 90% of the monomers used, which can be precipitated with methanol.
  • Analysis of the copolymer shows a proportion of 71% by weight of MAN and 29% by weight of VCl 2 .
  • the softening temperature (tg) is 85 ° C.
  • the viscosity of a 20% butanone solution, measured at 20 ° C., is 8.5 mPa. s.
  • the polymer solution obtained in this way can be diluted to 20% by weight with butanone and with a solution of 20% by weight of a copolymer of 80% by weight vinylidene chloride and 20% by weight acrylonitrile (trade name Saran® F 310) in a ratio of 1 +9 up to the ratio 9 + 1 can be mixed without gaps. Even after standing for several days, the mixtures show no signs of incompatibility with one another, for example through the formation of two phases or through clouding of the solutions.
  • copolymers are miscible in butanone with a solution of 20% by weight of a copolymer of 80% by weight vinylidene chloride and 20% by weight acrylonitrile in all ratios.
  • Solutions are poured onto a film made of polyethylene terephthalate and contain, as a binder, a copolymer which has been obtained by the process given in Example 1 (copolymer 1), in a mixture with a solution of a copolymer of 80% by weight vinylidene chloride and 20% by weight. -% acrylonitrile (copolymer 2) (solvent: butanone).
  • the butanone solutions contain 20% by weight of the specified binder mixture.
  • a butanone-soluble diazonium compound (4-morpholino-, 2,5 diisopropoxy-benzenediazonium tetrafluoborate) with 5% by weight, based on the solid binder, is used as the photosensitive compound.
  • the solutions are poured onto a 100 I lm thick film of Polyäthylentrerephthalat so as to obtain after drying a layer of about 8 g / m 2. Drying increases from 50 ° C to 130 ° C in the course of 90 seconds in circulating air.
  • Table 1 summarizes various binder compositions and the properties of the vesicular materials obtained therefrom.
  • D min and D max denote the density in the image-free or exposed areas and developed at 90 ° C. for 2 seconds, measured with the Macbeth Transmission Densitometer TD 528.
  • the thermal image stability denotes the remaining density of a fully exposed film strip developed at 90 ° C. for 2 seconds after storage for 1 hour at 80 ° C., expressed in% of the original density.
  • the maximum resolution denotes the number of lines that can still be read / mm after development at 90 ° C.
  • the image haze denotes the degree of haze in the non-image area, which is measured after the exposure of the non-image areas.
  • the film samples are first exposed to a development temperature of 90 ° C. for a period of 2 seconds, then fully exposed and again held at a temperature of 50 ° C. for a period of 20 seconds.
  • the haze to be measured is given as an image haze.
  • copolymers according to Examples 2 and 3 are diluted to 20% by weight with butanone and mixed with 20% by weight solutions of copolymer 2. After adding the diazonium salt and a few drops of the leveling agent, the solutions are cast into films on polyester films.
  • This hardening consists in an increased exposure to heat. This can be done by increasing the heat transfer, for example by contact with metallic surfaces or by increasing the air circulation. It can also be achieved by extending the drying time. Finally, an increase in the drying temperature can also be used, but only within the limits permitted by the presence of the diazonium salt.
  • copolymers and blends are used to produce layers which are similar to those of Examples 1 to 5, in order to illustrate the change in properties of the layers, as can only be achieved by curing.
  • curing was achieved in part by increasing the heat transfer as a result of a higher air speed in the dryer, in part curing was also achieved by increasing the drying time or by increasing the temperature in the last drying phase.
  • copolymers are miscible in butanone with a solution of 20% by weight of a copolymer of 80% by weight vinylidene chloride and 20% by weight acrylonitrile in all ratios.
  • the butanone solutions contain 20% by weight of the specified binder mixture.
  • a butanone-soluble diazonium compound (4-morpholino-, 2,5-dimethoxybenzene diazonium tetrafluoborate) with 5% by weight, based on the solid binder, is used as the photosensitive compound.
  • Drying increases from 50 ° C to 130 ° C over 90 seconds.
  • the layer is hardened by additional heating on a metal roller of 125 ° C. for a period of approx. 60 seconds.
  • Table 3 summarizes various binder compositions and the properties of the vesicular materials obtained therefrom.
  • D min and D max denote the density in the image-free or exposed areas and developed at 110 ° C. for 2 seconds, measured with the Macbeth Transmission Densitometer TD 528.
  • the thermal image stability denotes the remaining density of a fully exposed film strip developed at 110 ° C. for 2 seconds after storage for 1 hour at 80 ° C., expressed in% of the original density.
  • the image haze denotes the degree of haze in the non-image area, which is measured after the exposure of the non-image areas.
  • the film samples are fully exposed and kept at a temperature of 60 ° C. for 20 seconds.
  • the haze to be measured is given as an image haze.
  • Solutions are poured onto a 100 ⁇ m thick film of polyethylene terephthalate which contain, as a binder, a copolymer which has been obtained by the process given in Example 6, in a mixture with a solution of a copolymer of 80% by weight vinylidene chloride and 20% by weight.
  • % Acrylonitrile (copolymer 2) (solvent: butanone).
  • the layer is dried and cured according to the method given in Example 8.
  • Table 4 summarizes various binder mixtures and the properties of the vesicular materials obtained therefrom.
  • the layer is cured after drying as indicated in Example 8.
  • Table 5 summarizes various binder mixtures and the properties of the vesicular materials obtained therefrom.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Claims (10)

1. Matériel d'enregistrement photosensible pour le procédé vésiculaire constitué par une couche appliquée sur un support approprié, comprenant un liant et un composé photosensible, caractérisé en ce que le matériel d'enregistrement contient comme liant un copolymère de méthacrylonitrile et de chlorure de vinylidène soluble dans la butanone ou est constitué par ce produit.
2. Matériel d'enregistrement selon la revendication 1, caractérisé en ce qu'il comprend comme liant un copolymère de méthacrylonitrile et de chlorure de vinylidène, soluble dans la butanone, en combinaison avec un copolymère de chlorure de vinylidène et d'acrylonitrile avec lequel il est miscible dans la butanone.
3. Matériel d'enregistrement selon la revendication 2, caractérisé en ce que le liant est composé de 80 à 40 parties en poids d'un copolymère de méthacrylonitrile et de chlorure de vinylidène et de 20 à 60 parties en poids d'un copolymère de chlorure de vinylidène et d'acrylonitrile.
4. Matériel d'enregistrement selon les revendications 1 et 2, caractérisé en ce que le copolymère de méthacrylonitrile et de chlorure de vinylidène comprend de 80 à 40 parties en poids de méthacrylonitrile, et présente une température de transition vitreuse comprise entre 80 et 130° C.
5. Matériel d'enregistrement selon les revendications 1 à 4, caractérisé en ce que le liant comprend un copolymère de méthacrylonitrile et de chlorure de vinylidène présentant dans une solution à 20% dans la butanone, mesurée à 20° C, une viscosité comprise entre 5 et 15 mPa - s.
6. Matériel d'enregistrement selon les revendications 1 à 5, caractérisé en ce que le liant est un mélange de 45 parties en poids d'un copolymère de 70% en poids de méthacrylonitrile et de 30% en poids de chlorure de vinylidène, et de 55 parties en poids d'un copolymère de 80% en poids de chlorure de vinylidène et de 20% en poids d'acrylonitrile.
7. Matériel d'enregistrement selon les revendications 1 à 5, caractérisé en ce que le liant est un mélange de 60 parties en poids d'un copolymère de 77% en poids de méthacrylonitrile et de 23% en poids de chlorure de vinylidène, et de 40 parties en poids d'un copolymère de 80% en poids de chlorure de vinylidène et de 20% en poids d'acrylonitrile.
8. Matériel d'enregistrement selon les revendications 1 à 5, caractérisé en ce que le liant comprend 80 parties en poids d'un copolymère de 70% en poids de méthacrylonitrile et de 30% en poids de chlorure de vinylidène et 20 parties en poids d'un copolymère de 80% en poids de chlorure de vinylidène et de 20% poids d'acrylonitrile.
9. Matériel d'enregistrement selon les revendications 1 à 5 caractérisé en ce que le liant comprend 40 parties en poids d'un copolymère de 75% en poids de méthacrylonitrile et de 25% en poids de chlorure de vinylidène et 60 parties en poids d'un copolymère de 80% de chlorure de vinylidène et de 20% d'acrylonitrile.
10. Matériel d'enregistrement selon les revendications 1 à 5, caractérisé en ce que le liant comprend 80 parties en poids d'un copolymère de 60% en poids de méthacrylonitrile et de 40% en poids de chlorure de vinylidène et 20 parties en poids d'un copolymère de 80% de chlorure de vinylidène et de 20% d'acrylonitrile.
EP81102626A 1980-04-16 1981-04-08 Matériel vésiculaire sensible à la lumière Expired EP0038016B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3014538 1980-04-16
DE19803014538 DE3014538A1 (de) 1980-04-16 1980-04-16 Lichtempfindliches vesicularmaterial

Publications (2)

Publication Number Publication Date
EP0038016A1 EP0038016A1 (fr) 1981-10-21
EP0038016B1 true EP0038016B1 (fr) 1983-07-06

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ID=6100137

Family Applications (1)

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EP81102626A Expired EP0038016B1 (fr) 1980-04-16 1981-04-08 Matériel vésiculaire sensible à la lumière

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US (1) US4339520A (fr)
EP (1) EP0038016B1 (fr)
JP (1) JPS56158332A (fr)
DE (2) DE3014538A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4811925A (en) * 1986-06-23 1989-03-14 Tachi-S Co. Ltd. Slide rail
JP2527476B2 (ja) * 1989-04-28 1996-08-21 ダイセル化学工業株式会社 光情報記録媒体
US5443938A (en) * 1992-09-25 1995-08-22 Brother Kogyo Kabushiki Kaisha Photosensitive printing member having ink-receptive capillary structures in the support and photosensitive layer

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3032414A (en) * 1956-11-19 1962-05-01 Kalvar Corp System of photographic reproduction
US3161511A (en) * 1962-02-15 1964-12-15 Kalvar Corp Methacrylonitrile vehicle for vesicular photography and method of using same
CA944603A (en) 1969-09-10 1974-04-02 Kalvar Corporation Vesicular films containing polymethacrylonitrile vehicle
US3620743A (en) * 1969-12-15 1971-11-16 Norman T Notley Vehicles for vesicular photographic materials
US3622336A (en) * 1970-01-27 1971-11-23 Norman Thomas Notley Vesicular light-sensitive materials comprising a copolymer of chloroacrylonitrile and methacrylonitrile
US3661589A (en) * 1970-02-18 1972-05-09 Norman T Notley Interfacial vesicular print materials and methods of preparation
GB1483641A (en) 1974-07-29 1977-08-24 Kalvar Corp Light-sensitive vesicular mediums
DE2438157A1 (de) * 1974-08-08 1976-02-19 Kalvar Corp Lichtempfindliches vesikularmaterial
CA1080535A (fr) 1975-03-19 1980-07-01 John C. Mcdaniel Methode de production d'une image directe dans un materiel photographique vesiculaire a double exposition par pretraitement a l'aide d'un fluide aqueux
JPS5437724A (en) * 1977-08-30 1979-03-20 Mitsubishi Chem Ind Foam photographyysensitive member

Also Published As

Publication number Publication date
DE3160554D1 (en) 1983-08-11
US4339520A (en) 1982-07-13
EP0038016A1 (fr) 1981-10-21
DE3014538A1 (de) 1981-10-22
JPS56158332A (en) 1981-12-07

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