US3736139A - Heat and light stabilization of photosensitive elements containing poly-halogenated hydrocarbons,n-vinylcarbazoles and difurfurylidene pentaerythritols - Google Patents

Heat and light stabilization of photosensitive elements containing poly-halogenated hydrocarbons,n-vinylcarbazoles and difurfurylidene pentaerythritols Download PDF

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Publication number
US3736139A
US3736139A US00213536A US3736139DA US3736139A US 3736139 A US3736139 A US 3736139A US 00213536 A US00213536 A US 00213536A US 3736139D A US3736139D A US 3736139DA US 3736139 A US3736139 A US 3736139A
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light
difurfurylidene
positive
photosensitive elements
vinylcarbazoles
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US00213536A
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English (en)
Inventor
H Yamashita
N Sekikawa
H Ono
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds

Definitions

  • the present invention relates to a new image forming process which shows a positive response and by which stable black images are produced.
  • the present invention provides a positive photographic system treated by a dry treatment which is not subject to the faults of the prior art.
  • the basic components of the photosensitive element are: (a) polyhalogenated hydrocarbon; (b) N-vinylcarbazole and (c) difurfiurylidene pentaerythritol.
  • This photosensitive element is prepared by dispersing these components as discrete globules in a water soluble binder and applying the dispersion onto a suitable support.
  • hydroquinone or resorcinol derivatives may be used in order to improve shelf-life, and sensitizers such as ferrocene and anthraquinone derivatives may be added.
  • Positive images can be obtained by treating the photosensitive element having such composition by three steps: (1) image-wise exposure; (2) heating; and (3) blanket exposure.
  • image-wise exposure For example, when the sensitive element is exposed to light for 5 seconds through a positive at a distance of 30 cm. from a 250 w. high pressure mercury arc lamp, heated at C. for 10 seconds and exposed again to light for 10 seconds by a mercury arc lamp, positive images having a black color on a yellow background are obtained.
  • the light strength needed varies with kinds of light wavelengths and cannot clearly be defined.
  • the lightsensitive material of the present invention largely depends on the light strength and does not form color unless the light strength is higher, even though the exposure time is prolonged.
  • the critical intensity (Ic) is determined on the lightstrength needed to show the density of Fog +0.1 when exposed for a certain period of time, e.g., 25 seconds, by varying the light wave lengths and the light-strength as shown in the attached figure. Ic is a minimum lightstrength and varies somewhat with the wave lengths employed.
  • 1c ranges from 0.1)(10 erg/cm. sec to 1 10 erg/ cm. sec and is 'sufiicient so long as it is more than the above range, for example, at least 10 erg/cm. sec is necessary on the light of the wave length having the highest sensitivity.
  • the strength of the first and second exposure is within the above range.
  • the short heating time is desirable, although the heating temperature is high.
  • the resulting images hardly change even though left in a light room.
  • the light room is used for investigating the change of the photo-sensitive element after treatment by the scattered light from the sun in a room.
  • Such a positive response is obtained when difurfurylidene pentaerythritol is used together with a water soluble binder.
  • This invention provides a black image obtained by positive working, which is a simplified dry process using heat and light.
  • the polyhalogenated hydrocarbon is selected from the group of the compounds which produce free radicals or IOIlS upon exposure to light of a suitable wavelength.
  • polyhalogenated hydrocarbon examples include carbon tetrabromide (CBr hexachloroethane (C Cl and iodoform (CHI
  • CBr hexachloroethane C Cl and iodoform
  • CHI carbon tetrabromide
  • water soluble substances such as gelatin, polyvinyl alcohol, casein, starch, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinyl pyrrodidone and polyethyleneglycol.
  • the molecular weight for the binder is thousands to hundred thousands, preferably 20,000 to 100,000.
  • composition of the mandatory materials are as follows:
  • the ratio of the N-vinylcarbazole/polyhalogenated hydrocarbon is 50/ l to 1/5, preferably /1 to 1/5.
  • the ratio of the N vinylcarbazole/difurfurylidene pentaerythritol is 100/1 to 1/10, preferably /1 to 1/2.
  • the ratio of the binder/light-sensitive material is 1/100 to 20/1, preferably l/10 to 5/1.
  • Example 1 An acetone solution of 5 g. of N-vinylcarbazole was added to 50 ml. of a 16% aqueous gelatin solution. The mixture was stirred at 70 C. for 2 minutes with a homomixer to finely disperse the N-vinylcarbazole in the gelatin. After adding 4 g. of carbon tetrabromide and a dichloroethane solution of 0.5 g. difurfurylidene pentraerythritol, the mixture was similarly dispersed. The amount of acetone 5 ml., and the amount of dichloroethane is 5 ml. The resulting dispersion was applied to baryta paper to provide a photosensitive element after drying.
  • a black image on a light yellow background was obtained by exposing this photosensitive element to light for 10 seconds through a positive at a distance of 30 cm. from a 250 w. super high pressure mercury arc lamp, heating at 100 C. for 10 seconds and exposing further for 10 seconds by a mercury arc lamp.
  • a black image on a yellow background could be obtained by leaving the element in a light room and omitting the last exposure by the mercury arc lamp. The resulting images hardly changed in a light room.
  • the photosensitive element was treated by the method described in US. Patent 3,476,562, 1.9-, a, bla k i ag 91 a ye low ba g und cou d be 4 obtained by exposing for 10 seconds through a photographic positive at a distance of 35 cm. from a 300 w. incandescent electric lamp. But the yellow background changed into brown color in a light room, which meant the fixing had not been carried out completely.
  • Example 2 G N-vinylcarbazole 5 Carbon tetrabromide 4 Difurfurylidene pentaerythritol 0.5 p-Bis(Z-tetrahydropyranyloxy) benzene 0.25
  • a photosensitive element was produced by dispersing the abovementioned components in an aqueous gelatin solution by the same procedure as in Example 1.
  • Example 3 A photosensitive element was produced substituting polyvinyl alcohol for the gelatin in Example 2. By carrying out the same exposing and heating treatments as in Example 2, a black image on a light yellow background was obtained.
  • Example 4 The same result as in Example 1 was obtained when iodoform was used instead of carbon tetrabromide in Example 1.
  • Example 5 G N-vinylcarbazole 5 Carbon tetrabromide 2 Hexachloroethane l Difurfurylidene pentaerythritol 0.5
  • a stable positive image which hardly changed in a light room was obtained by treating a photosensitive element prepared by dispersing the abovementioned components in an aqueous solution of polyvinyl alcohol and thereafter heating and exposing as in Example 1.
  • the most important commercial embodiments are as follows. Duplicating by micro-film image or slide-film image. Duplication can be carried out on both of a positive and negative image, and generally on the positive image.
  • the binders are gelatin, polyvinyl alcohol, gum arabic, polyvinylpyrrolidone, etc.
  • the globule size is 0.1 to 30 preferably 0.5 to 10;.
  • an image forming process by dry treatment which comprises imagewise exposing a photosensitive element comprising a support having thereon a polyhalogenated hydrocarbon and N-vinylcarbazole dispersed as discrete globules in a water-soluble binder to ultraviolet rays or visible rays and heating, the improvement comprising said photosensitive element containing difurfury'lidene pentaerythritol and the improvement further comprising exposing uniformly said imagewise exposed element to ultraviolet rays or visible rays after the heating thereof, by which a black positive image is obtained; said polyhalogenated hydrocarbon having the following general formula;
  • R is a hydrogen atom, X, COOR' or R is H, CH or C H X is Cl, Br or I; and m and n are an integer of 2 or 3.
  • water soluble binder is selected from the group consisting of casein, starch, hydroxyethyl cellulose,

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00213536A 1970-12-29 1971-12-29 Heat and light stabilization of photosensitive elements containing poly-halogenated hydrocarbons,n-vinylcarbazoles and difurfurylidene pentaerythritols Expired - Lifetime US3736139A (en)

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JP45121450A JPS4920979B1 (en, 2012) 1970-12-29 1970-12-29

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US3736139A true US3736139A (en) 1973-05-29

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US (1) US3736139A (en, 2012)
JP (1) JPS4920979B1 (en, 2012)
DE (1) DE2165374A1 (en, 2012)
FR (1) FR2120988A5 (en, 2012)
GB (1) GB1358107A (en, 2012)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4077805A (en) * 1974-10-25 1978-03-07 Shirow Asakawa Light-sensitive composition containing antioxidant
US4399209A (en) * 1981-11-12 1983-08-16 The Mead Corporation Transfer imaging system
US4416966A (en) * 1982-08-25 1983-11-22 The Mead Corporation Capsular imaging system comprising decolorizing agent
US4440846A (en) * 1981-11-12 1984-04-03 Mead Corporation Photocopy sheet employing encapsulated radiation sensitive composition and imaging process
US4482624A (en) * 1983-02-15 1984-11-13 The Mead Corporation Photosensitive material employing encapsulated radiation sensitive composition and process for improving sensitivity by sequestering oxygen
US4508807A (en) * 1983-07-11 1985-04-02 Mead Corporation Photosensitive material employing encapsulated radiation sensitive composition and a transparentizable image-receiving layer
US4535050A (en) * 1983-07-18 1985-08-13 The Mead Corporation Peeling development of photosensitive materials employing microencapsulated radiation sensitive compositions
US4562137A (en) * 1982-12-30 1985-12-31 The Mead Corporation Photosensitive material employing encapsulated radiation sensitive composition
US4822714A (en) * 1981-11-12 1989-04-18 The Mead Corporation Transfer imaging system
US4903991A (en) * 1983-07-18 1990-02-27 The Mead Corporation Document security system

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5315153A (en) * 1976-07-27 1978-02-10 Canon Inc Hologram

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1093724A (en) * 1964-03-12 1967-12-06 Warren S D Co Photographic mediums based on furfurylidens

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4077805A (en) * 1974-10-25 1978-03-07 Shirow Asakawa Light-sensitive composition containing antioxidant
US4399209A (en) * 1981-11-12 1983-08-16 The Mead Corporation Transfer imaging system
US4440846A (en) * 1981-11-12 1984-04-03 Mead Corporation Photocopy sheet employing encapsulated radiation sensitive composition and imaging process
US4822714A (en) * 1981-11-12 1989-04-18 The Mead Corporation Transfer imaging system
US4416966A (en) * 1982-08-25 1983-11-22 The Mead Corporation Capsular imaging system comprising decolorizing agent
US4562137A (en) * 1982-12-30 1985-12-31 The Mead Corporation Photosensitive material employing encapsulated radiation sensitive composition
US4482624A (en) * 1983-02-15 1984-11-13 The Mead Corporation Photosensitive material employing encapsulated radiation sensitive composition and process for improving sensitivity by sequestering oxygen
US4508807A (en) * 1983-07-11 1985-04-02 Mead Corporation Photosensitive material employing encapsulated radiation sensitive composition and a transparentizable image-receiving layer
US4535050A (en) * 1983-07-18 1985-08-13 The Mead Corporation Peeling development of photosensitive materials employing microencapsulated radiation sensitive compositions
US4903991A (en) * 1983-07-18 1990-02-27 The Mead Corporation Document security system

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Publication number Publication date
GB1358107A (en) 1974-06-26
DE2165374A1 (de) 1972-07-13
JPS4920979B1 (en, 2012) 1974-05-29
FR2120988A5 (en, 2012) 1972-08-18

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