Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
  • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
  • C07C309/17—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
  • C08F20/62—Monocarboxylic acids having ten or more carbon atoms; Derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F4/00—Polymerisation catalysts
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording-members for original recording by exposure, e.g. to light, to heat or to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/10—Bases for charge-receiving or other layers
  • G03G5/105—Bases for charge-receiving or other layers comprising electroconductive macromolecular compounds
  • G03G5/108—Bases for charge-receiving or other layers comprising electroconductive macromolecular compounds the electroconductive macromolecular compounds being anionic

Definitions

• This invention relates to the use of bisulfite regulated oligomers as conductive agents, particularly to their use as conductive agents for the conductive barrier coating on photoelectrostatic copying paper or other photoelectrostatic recording members.
• the conductive agent in the conductive barrier coating of the recording member in the photoelectrostatic copying process serves to give electrical conductivity to the non-metallic base such as a sheet of paper which has high electrical resistance.
• the non-metallic base is coated on both sides with a conductive barrier coating.
• a photosensitive coating-composed of a photosensitive material, such as zinc oxide, a binder, such as an alkyd resin, and a sensitizing agent, such as an organic dye- is applied to one side of the base atop of the conductive barrier coating.
• This latter coating is composed of a conductive agent, usually in conjunction with tack reducing materials, such as pigments, waxes or polymers. If the base is porous, the two conductive barrier coatings may be connected.
• the photosensitive coating layer is given a blanket negative charge in the dark, electrostatically, by passing a corona unit with a high negative voltage over the recording member.
• the material to be copied is then illuminated and, by mean of lenses and mirrors, its image projected onto the recording members photosensitive surface. Where this image is white, light strikes the negatively charged photosensitive layer and causes this negative charge to drain off through the conductive barrier coating. Where this image is dark, no light strikes the negatively charged photosensitive layer and these areas remain charged.
• toner particles To make this image visible and permanent, positively charged and colored particles, called toner particles, are brought in contact with the recording member.
• the toner particles may be dusted onto the recording member in powder form, as in the dry toner process, or in a solvent dispersion through which the recording member passes.
• the toner particles are fused to the recording member, by heating, if a dry toner process is used, or by air evaporation of the solvent, ifa solvent dispersion of the toner is used.
• the conductive agent must be highly conductive over the broad range of temperature and humidity conditions at which copying machines are operated. This high conductivity permits the charge to drain quickly and completely from those areas of the conductive barrier coating where the light strikes and to produce sharp copies of the original and to prevent back marking and reverse imaging. Naturally, also high condctivity is economically desirable; since satisfactory results may be obtained with the application of less material per unit area.
• a solution or suspension of the conductive agent which has a low viscosity, particularly at high solids concentration, for ease of application and uniformity of coating.
• Other desired properties of the conductive agent are resistance to solvent, specifically in a solvent based copying process, in order to prevent solvent penetration of the recording member; neutral color so as not to prevent preparation copies from being white where desired; and ease of preparaion in an aqueous medium. This later attribute permits the use of the conductive agent directly and avoids the necessity of removing solvent.
• M is a water soluble cation such as an alkali metal or ammonia M is an alkali meal or ammonium; R and R are hydrogen or methyl; X is a CN or CONl-l group; a b is from 10 to 60, preferably from 15 to 40; b/a b is 0.1 to 0.4, preferably from 0.l5 to 0.35
• the acid form of the above oligomers may be prepared by the reductive polymerization technique illustrated in U.S. Pat. No. 3,646,099 to Leland E. Dannals, entitled Oligomers.”
• the acid form of the oligomer is thereafter neutralized to form the water soluble conductive agents of the invention.
• alkaline materials which neutralize the acid oligomer and form a water soluble oligomer salt may be used. These include alkali metal and ammonium hydroxides and carbonates. Most preferable are salts of the alkali metals having an atomic number of 19 or more. As a practical matter, of these, potassium salts are most desirable.
• the conductive barrier coating may be conveniently applied to the base by any of the conventional techniques known to those skilled in the art. Since the bisulfate regulated oligomers may be prepared in an aqueous solution and since the reaction goes to substantially complete conversion, the polymerizate, after neutralization, may be used directly as the coating solution. No intermediate processing, e.g., the removal of solvent or unreacted monomer, is necessary.
• Extenders such as other polymers and pigments, may be added to improve the properties of the coating and decrease its cost.
• examples of'pigments which may be used are clay, titanium dioxide, calcium carbonate, hydrated alumina and talc.
• Qther polymers both conductive and non-conductive, include carboxylated SBR latexes, acrylate latexes and water soluble polycationic polymers. Starch may also be added.
• Ammonium stearate, calcium stearate and carbowax are examples of tack reducing agents which may be added.
• EXAMPLE I A typical laboratory preparation of the acid of the oligomers is performed in a one-quart reactor which is fitted with an agitator, a liquid phase thermometer, a reflux condenser, an additional funnel, and a gas induction tube leading into the vapor phase. This ensemble is in a thermostated bath at 31.8C.
• Nitrogen is allowed to flow slowly (ca. 100 cc/ min.) into the reactor through the gas induction tube.
• 0.25 ml. 1 percent aqueous (NH S O is added over about a three hour period through the addition funnel.
• the weight of the clear reaction product is 269.2 g. it has 39.2 percent solids which indicates 99.0 percent conversion. Its viscosity is 7,700 cps.
• EXAMPLE Ill Other acid forms of the oligomers useful in the invention having the following formulas are prepared using 3.47 grams of Nal-lSO as the initiator and 0.04 grams of (Ni- 0 8 0 as the activator per mole of monomers. ln all runs the conversion is over 98 percent. The viscosity of an aqueous solution having about 35 percent solids is shown:
• EXAMPLE IV This example shows the effect of storage on reaction product viscosity and also on the effect of the initiator action on viscosity. All reactions are over percent conversion and the oligomers are H-(acrylonitrile) (acrylic acid), SO M. The following table shows the results obtained:
• EXAMPLE V Using the general procedure in Example 1, several other oligomers of the invention, of the type described by the general formula, H-(acrylonitrile),,-(acrylic acid) SO Na, are prepared. DO (degree of oligomerization), is given by (a b but is calculated from moles of monomer/gFW of reducing initiator. In this work D0 is varied from 16 to 60, the mole fraction of acrylic acid b/(a b from 0.500 to 0.0 and the percent solids from 10 to 60 percent.
• DO degree of oligomerization
• EXAMPLE VI This example describes the preparation of, H- (acrylonitrile), -(acrylic acid) ,,SO Na and its potassium salt in which almost all of the acrylic acid groups are neutralized with potassium hydroxide.
• a one gallon reactor fitted in a like manner to the quart reactor of Example I is charged with 1707 g. water, 265 g. acrylonitrile, 1080 g. acrylic acid, and 52 g. NaHSO
• the reactor is placed in a water bath thermostated at 29.8" C. and a nitrogen stream flows through the vapor phase of the reactor.
• the initiator, l g. (NHQ S O in 68 g. water, is added slowly so that g. of the solution are in the reactor after 4 hours.
• the temperature of the reactants rises to 41 C.
• the reaction stands overnight and has 44.9 percent solids and a viscosity of 74,000 cps.
• 33 percent Aqueous KOH solution is added to the reaction product in quantity sufficient to neutralize 95 percent of the acrylic acid present.
• This salt solution is without haze or tint, has 37.8 percent solids, 1300 cps. viscosity and 6.5 pH.
• EXAMPLE VII Using the procedure described in the previous example, except the oligomer H-(acrylonitrile) -(acrylic acid), SO Na is prepared.
• the reaction product has 44.6 percent solids, and 4950 cps. viscosity and is clear and colorless.
• a salt solution of the oligomer is obtained. This is clear and colorless, has 37 percent solids, 230 cps. viscosity and 6.4 pH.
• the table indicates the values of X, a b, a/a b, and the specific resistance in megohms at 10 percent and 50 percent relative humidity (before and after the slash mark, respectively):
• EXAMPLE IX This example illustrates the effect of the cationic group on the conductivity of the dried oligomer film.
• the acid form of the oligomer having the formula: N(CH CHCOOH) CHCN) SO Na, are neutralized with the alkali metal and ammonium hydroxides to a pH of 7.5 and coated on a West Virginia rosin sized electrofax base stock.
• the sheets are cut up, conditioned at the desired relative humidities and resistivity readings taken.
• the results are shown in the following The above data clearly show that the larger cationic groups are most advantageous. From the commercial standpoint potassium is clearly most preferable (because of its availability), since no appreciable improvement is obtained with the larger cations.
• the coated sheets with the zinc oxide photosensitive top coating were aged for 45 days at 72 F. and 50 percent relative humidity. These sheets imaged well using the laboratory SCM 33 copying machine. This indicates that there is no oligomer migration during storage of the sheet.
• Films of this oligomer have been aged at 72 F. and 50 percent relative humidity for 5 weeks with no apparent migration within the film or any detrimental effects to the film. Additionally, the film has good solvent resistance to mineral spirits and toluene and is odorless.
• a photoelectrostatic recording member which comprises (1) a non-metallic base sheet; (2) a conductive barrier coating containing an oligomer having the formula H[CH CR'COOM],, [CH CR X],,-SO M' wherein M and M are water soluble cations; R' and R are hydrogen or methyl; X is a CN or a CONI-I group; a +b is from 10 to 60 and bla b is from 0.1 to
• h i M d M are lk fi metaq or ammonium 5.
• the photoelectrostatic recording member ofclaim groups; R and R are hydrogen; and a b is from to 1 wherein said is Paper- 30. 1

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Cited By (2)

Citations (2)

• 1968
  • 1968-10-04 AT AT909670A patent/AT303515B/de not_active IP Right Cessation
• 1970
  • 1970-05-01 US US00043655A patent/US3719485A/en not_active Expired - Lifetime

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