US3887377A - Antistatic photographic light-sensitive materials - Google Patents
Antistatic photographic light-sensitive materials Download PDFInfo
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- US3887377A US3887377A US380795A US38079573A US3887377A US 3887377 A US3887377 A US 3887377A US 380795 A US380795 A US 380795A US 38079573 A US38079573 A US 38079573A US 3887377 A US3887377 A US 3887377A
- Authority
- US
- United States
- Prior art keywords
- antistatic
- photographic light
- cellulose
- sensitive material
- light sensitive
- 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
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- 229920000159 gelatin Polymers 0.000 claims description 7
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- 108010010803 Gelatin Proteins 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 claims description 6
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- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
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- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
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- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
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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
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/85—Photosensitive materials characterised by the base or auxiliary layers characterised by antistatic additives or coatings
Definitions
- the present invention relates to a method for rendering a photographic light-sensitive material antistatic, and, more particularly, it relates to an antistatic photographic light-sensitive material comprising at least one light-sensitive silver halide emulsion layer and at least one non-gelatin containing antistatic backing layer.
- photographic light-sensitive materials comprise a support having provided on one or both surfaces thereof a light-sensitive photographic emulsion layer via a subbing layer capable of strongly adhering the support to the photographic emulsion layer.
- the support typically comprises a film of a poly-ozolefin (e.g., polyethylene, polystyrene, etc. a cellulose ester (e.g., cellulose triacetate), a polyester (e.g., polyethylene terephthalate etc.), paper, synthetic paper, or a sheet laminated on both sides with a poly-a-olefin or like synthetic resin.
- a poly-ozolefin e.g., polyethylene, polystyrene, etc.
- a cellulose ester e.g., cellulose triacetate
- a polyester e.g., polyethylene terephthalate etc.
- paper synthetic paper
- photographic light-sensitive materials having an emulsion layer coated on both sides of a support there can be illustrated, e.g., an X-ray film for direct use.
- a photographic emulsion is coated only on the one side of the support. Therefore, in the latter case, the photographic materials possess a photographic emulsion-free surface, i.e., the surface of a support itself, which surface is usually called the back surface of the photographic light-sensitive material.
- photographic light-sensitive materials comprise, as is described above, an insulating support and a photographic layer
- electrostatic charges tend to accumulate during the steps of producing the photographic light-sensitive materials and upon the use thereof due to contact friction with the surface of the same or different substances, or due to delamination.
- These accumulated electrostatic charges cause a number of problems.
- the light-sensitive emulsion layer will be sensitized by the discharge of the accumulated electrostatic charges, which results in the formation of dot-like spots or branched or feather-like line marks upon development. These are commonly called static marks, and seriously or, in some cases, completely, spoil the commercial value of the photographic films.
- electrostatic charge is generated by contact friction between the photographic film and a roller as by the separation of the support surface from an opposing emulsion-coated surface in winding and unwinding steps.
- electrostatic charge is generated by delamination of the base surface form the emulsioncoated surface in winding and unwinding steps under sufficient humidity to cause adhesion of the photographic films to each other, by contact friction of movie films with mechanical portions of a camera and during the delamination of the base surface from the emulsion surface upon photographing and changing movie films, or by the contact and separation of X-ray film and mechanical portions in an automatic camera for X-ray films or fluorescent-sensitizing paper.
- electrostatic charge is also generated due to the contact witha packing material.
- one method for directly providing a photographic film support with an antistatic property comprises incorporating the compounds as described above in a high molecular weight support or applying such compounds or substances to the surface of the support.
- an antistatic agent is independently applied as a backing layer to the surface or in combination with a high molecular weight substance such as gelatin, polyvinyl alcohol, cellulose acetate or the like.
- R and R which may be the same or different, each represents an aliphatic hydrocarbon residue having 1-22 carbon atoms, the sum of the carbon atoms of R and R being 6-40, A represents a divalent aliphatic hydrocarbon residue having a total of 4-8 carbon atoms, M represents a hydrogen atom, a metal atom or a quaternary ammonium salt, and m represents a number corresponding to the valence of M.
- the generation of static marks can be markedly reduced by using the compound represented by the above-illustrated general formula in accordance with the invention applied to a backing or surface layer or incorporated in a backing or surface layer at the exterior of the element, which static marks result from the contact between the emulsion-coated surface of a light-sensitive material and the backing layer thereof and contact between the emulsion-coated surface and a substance with which a photographic light-sensitive material generally comes into contact, such as a rubber, metal, plastic or a fluorescence-sensitizing paper (used for X-ray films).
- the compounds of the invention have the tendency that the charging or amount approaches zero with an increase in the amount of the compound added. Therefore, the feature of the compounds used in the invention is that electrification series can be freely controlled to zero or to the negative side by properly adjusting the amount of the compounds or by combining the compounds with an antistatic agent capable of positively charging the photographic material.
- the metallic atom there can be illustrated any of those metals which form a salt, such as the alkali metal atoms, e.g., Li, Na, K, etc., the alkaline earth metal atoms, e.g., Mg, Ca, and Ba, and Zn, Al and the like.
- the alkali metal atoms e.g., Li, Na, K, etc.
- the alkaline earth metal atoms e.g., Mg, Ca, and Ba
- Zn, Al and the like such as the alkali metal atoms, e.g., Li, Na, K, etc.
- the alkaline earth metal atoms e.g., Mg, Ca, and Ba
- Zn Al and the like.
- the compounds used in the present invention are used in an amount vof from abou't0.005 g to about 2.0
- g particularly preferably from 0.01 to 0.4 g, per 1 m of the photographic film base.
- this amount can be varied within the range set forth depending upon the kind of photographic film base, stratum structure, element, form, coating method, and the like.
- the compound used in the invention can be applied thereto by spraying or coating on the surface of a support or on the photographic layer of a photographic film after dissolving the compound in water, organic solvent(s), or a mixture thereof, or by immersing the support or photographic film in such a nongelatin containing solution, followed by drying.
- the compounds may also be used together with a binder.
- binders are cellulose derivatives such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose acetate phthalate, cellulose acetate succinate, cellulose tripropionate, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, or ethyl cellulose, and also synthetic polymers and copolymers of a polymerizable monomer such as styrene, vinyl ethers, vinyl esters, acrylic acid esters, vinyl ketones, vinyl chloride, acrylonitrile and maleic acid, etc., may be employed as a binder.
- the antistatic agent of the present invention can also be used in combination with other antistatic agents.
- various additives desired for various purposes such as a hardening agent, a lubricant, a matting agent, an antihalation dye, and the like.
- the compound used in the invention can be applied to filmshaped products of cellulose esters, polyesters, polystyrenes, polycarbonates, or vinyl resins such as polyethylene, polypropylene, etc., for antistatic purpose. They are suitable for non-photographic uses as well.
- Troubles due to electrostatic charging during the steps of producing photographic light-sensitive materials or upon use thereof can be remarkably reduced by the present invention.
- charging upon mounting a photographic film in a cassette or in a camera can be effectively prevented even under low humidity conditions, and the antistatic effect will not deteriorate with the passage of time.
- a photographic film to which the compound used in the invention has been applied has the feature that when the emulsion-coated surface is brought into contact with the back surface at elevated temperature and under high humidity they do not adhere to each other.
- the charging amount was measured by rolling a test piece, l l5 cm, with a rubber roller under a load of 380 g and at a rate of 33 cm/sec., then allowing it to fall in a Faraday cage.
- the reason why a rubber roller was used for estimating the charging amount is that rubber was considered to be representative of the substances above since it is essentially in the center of the electrification series with plastic, metal, paper, cotton, etc.
- the surface resistivity was measured by placing a test piece between brass electrodes 10 cm in length with an electrode gap of 0.14 cm (the portion of the electrodes in contact with the test sample were made of stainless steel) and measuring 1 minute values by means of an insulation resistance tester (MM-V-M type, made by Takeda Riken Kogyo K.K.).
- the static marks were produced on an unexposed film on a rubber sheet with the back surface of the film facing the rubber sheet by pressingthe assembly from above with a rubber roller followed by delamination.
- the charging amount and the surface resistivity were measured at 23C and 65 percent RH, whereas the static mark-generating test was conducted at 23C and 30 percent RH. Additionally, air conditioning for the test pieces was conducted for 1 day and 1 night under the aforesaid temperature and humidity conditions prior to testing.
- antistatic solution having the following composition to coat the sheet, directly followed by heat-drying in air at 120C for 30 minutes to form an antistatic layer of 0.3 micron in thickness.
- composition of the antistatic solution is a composition of the antistatic solution:
- Antistatic solution (I); a 5% by weight methanol solution of the compound of the present invention (Compound 5 illustrated before) Binder solution (11); a 5% by weight cellulose triacetate solution (mol weight about 80,000 solvent: methylene dichloridezmethanol 92z8 in weight ratio): 12 g Solvent (Ill); Phenol: 2 g Tetrachloroethane: 8 g Ethylene chloride: 70 g Solvent (1V); methanol 20 g (including the amount added to antistatic solution (1)) Antistatic solution (1) was weighed out in such amount that the content of the effective, antistatic ingredient contained therein became l, 3, 5 or 10 per cent based on the binder. To each weighed solution solvent (IV), binder solution (Il) and solvent (Ill) were added.
- Illustrated compound 5 Continuous Illustrated compound 10 t-C H l1 OCH CH CHSO Na Table 2 Antistatic Content of Charging Surface Agent Antistatic Amount Resistivity Agent Based (V) (ohm) on Binder by weight) Compound (5) 2 60 l X of the present inven- 4 -30 2 X 10 tion Compound (6) 2 l06 4 X 10 of the present inven- 4 45 6 X l0 tion Compound (10) 2 80 l X l0 of the present inven- 4 35 2 X l0 tion Comparative 2 3O 3 X l0' compound (A) Comparative 2 5 l X l0 compound (B) Comparative 2 50 2 X l0 compound (C) 4 22 3 X IO Comparative 2 l8 9 X 10" compound (D) Control 0 50 not less than As is clear from the results given in Table 2, the charge in the case of the comparative compounds was always positive, whereas the charge in the case of the compounds of the
- EXAMPLE 2 An antistatic solution having the following composition was applied to one surface of a cellulose acetate films (127 microns in thickness) to form a backing layer (0.3 micron in thickness) and a negative emulsion layer for cinema (10 microns in thickness) was provided on the opposite surface to prepare movie films.
- Binder solution ("1); a 0.3% by weight solution of cellulose triacetate (mol weight: about 80,000 solvent: methanol: ethylene chloride: tettachloroethane: phenol 8:70:8:2 in
- An antistatic photographic light-sensitive material having thereon a surface layer comprising a non-gelatin containing binder and an antistatic compound represented by the following general formula:
- R and R which may be the same or different, each represents an aliphatic hydrocarbon residue having 1-22 carbon atoms, the sum of carbon atoms or R and R being 6-40, A represents a divalent aliphatic hydrocarbon residue having 4-8 carbon atoms in total, M represents a hydrogen atom, a metal atom or a quaternary ammonium salt, and m represents a number corresponding to the valence of M.
- the antistatic photographic light sensitive material of claim 1 wherein the thickness of said layer ranges from about 0.2 p. to about 10 11..
- M is an alkali metal atom or an alkaline earth metal atom.
- antistatic photographic light sensitive material of claim 1 wherein said antistatic compound is present at from about 0.005 to about 2 g per 1 m of surface area of said material.
- said cellulose derivative is cellulose diacetate, cellulose triacetate, cellulose acetate .propionate, cellulose acetate butyrate, cellulose acetate phthalate, cellulose acetate succinate, cellulose tripropionate, carboxymethyl cellulose, hydroxye'thyl cellulose, hydroxypropyl cellulose, methyl cellulose, or ethyl cellulose and said synthetic polymer or copolymer is a polymer or copolymer of a polymeriazble monomer selected from the group consisting of styrene, vinyl ethers, vinyl esters, acrylic acid esters, vinyl ketones, vinyl chloride, acrylonitrile and maleic acid.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Laminated Bodies (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7354272A JPS4933630A (enrdf_load_stackoverflow) | 1972-07-22 | 1972-07-22 | |
| JP10648772A JPS5225250B2 (enrdf_load_stackoverflow) | 1972-10-24 | 1972-10-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3887377A true US3887377A (en) | 1975-06-03 |
Family
ID=26414685
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US380795A Expired - Lifetime US3887377A (en) | 1972-07-22 | 1973-07-19 | Antistatic photographic light-sensitive materials |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3887377A (enrdf_load_stackoverflow) |
| CA (1) | CA999465A (enrdf_load_stackoverflow) |
| DE (1) | DE2337392A1 (enrdf_load_stackoverflow) |
| FR (1) | FR2193994B1 (enrdf_load_stackoverflow) |
| GB (1) | GB1409849A (enrdf_load_stackoverflow) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4328280A (en) * | 1978-05-15 | 1982-05-04 | Minnesota Mining And Manufacturing Company | Suppression of spark discharges from negatively triboelectrically charged surfaces |
| US4610945A (en) * | 1983-12-15 | 1986-09-09 | Fuji Photo Film Co., Ltd. | Encapsulated toner having improved image-forming characteristics |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3415649A (en) * | 1963-07-01 | 1968-12-10 | Fuji Photo Film Co Ltd | Process for the production of light-sensitive material containing coating aids |
| US3525620A (en) * | 1966-01-05 | 1970-08-25 | Fuji Photo Film Co Ltd | Photographic light-sensitive element |
| US3756828A (en) * | 1971-03-11 | 1973-09-04 | Fuji Photo Film Co Ltd | Es photographic light sensitive material having good antistatic properti |
-
1973
- 1973-07-19 GB GB3453873A patent/GB1409849A/en not_active Expired
- 1973-07-19 CA CA176,819A patent/CA999465A/en not_active Expired
- 1973-07-19 US US380795A patent/US3887377A/en not_active Expired - Lifetime
- 1973-07-23 FR FR7326912A patent/FR2193994B1/fr not_active Expired
- 1973-07-23 DE DE19732337392 patent/DE2337392A1/de active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3415649A (en) * | 1963-07-01 | 1968-12-10 | Fuji Photo Film Co Ltd | Process for the production of light-sensitive material containing coating aids |
| US3525620A (en) * | 1966-01-05 | 1970-08-25 | Fuji Photo Film Co Ltd | Photographic light-sensitive element |
| US3756828A (en) * | 1971-03-11 | 1973-09-04 | Fuji Photo Film Co Ltd | Es photographic light sensitive material having good antistatic properti |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4328280A (en) * | 1978-05-15 | 1982-05-04 | Minnesota Mining And Manufacturing Company | Suppression of spark discharges from negatively triboelectrically charged surfaces |
| US4610945A (en) * | 1983-12-15 | 1986-09-09 | Fuji Photo Film Co., Ltd. | Encapsulated toner having improved image-forming characteristics |
Also Published As
| Publication number | Publication date |
|---|---|
| CA999465A (en) | 1976-11-09 |
| FR2193994B1 (enrdf_load_stackoverflow) | 1977-09-09 |
| DE2337392A1 (de) | 1974-02-07 |
| FR2193994A1 (enrdf_load_stackoverflow) | 1974-02-22 |
| GB1409849A (en) | 1975-10-15 |
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