US3544318A - Electroconductive paper - Google Patents

Electroconductive paper Download PDF

Info

Publication number
US3544318A
US3544318A US743634A US3544318DA US3544318A US 3544318 A US3544318 A US 3544318A US 743634 A US743634 A US 743634A US 3544318D A US3544318D A US 3544318DA US 3544318 A US3544318 A US 3544318A
Authority
US
United States
Prior art keywords
paper
polymer
electroconductive
ammonium chloride
weight
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
US743634A
Inventor
Jerry E Boothe
Merwin Frederick Hoover
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.)
Calgon Corp
Original Assignee
Calgon Corp
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 Calgon Corp filed Critical Calgon Corp
Application granted granted Critical
Publication of US3544318A publication Critical patent/US3544318A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00Coated paper; Coating material
    • D21H19/10Coatings without pigments
    • D21H19/12Coatings without pigments applied as a solution using water as the only solvent, e.g. in the presence of acid or alkaline compounds
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/10Bases for charge-receiving or other layers
    • G03G5/105Bases for charge-receiving or other layers comprising electroconductive macromolecular compounds
    • G03G5/107Bases for charge-receiving or other layers comprising electroconductive macromolecular compounds the electroconductive macromolecular compounds being cationic

Definitions

  • Electrocondnctive paper useful typically in making copies by an electrostatic process is made by incorporating therein a polymer comprising at least 90% monomers of the formula (CHFCHCHa)2 i i A where R is an alkyl group of 1 to 18 carbon atoms and -R is R or B-propionamido and A is an anion.
  • This invention relates to paper containing electroconductive materials.
  • it relates to paper rendered electroconductive by a layer or coating of electroconductive material, which paper is useful in various copying processes and devices.
  • Electroconductive paper may be used to distribute electrical stresses in various insulating products; see US. Pat. 3,148,107. Where electrically conductive paper is to be used for nonimpact printing, a substrate, backing, impregnation coating, or layer of electrically conductive material is usually constructed. See Vaurio and Fird, Electrically Conductive Paper for Nonimpact Printing, Tappi, December 1964, vol. 47, No. 12, pp. 163A-165A.
  • Various types of nonimpact printing processes are known as electrostatographic, electrophotographic, electrographic, Electrofax, and other processes. As a rule such processes call for the placement of an electric charge on the paper, which may be accomplished by a corona discharge, for example. The charge is, in most such processes, placed on the paper in darkness.
  • the paper may also contain a photo-responsive or photo-conductive layer or material, now popularly a specially treated zinc oxide, which causes the charge to be dissipated in an area where light strikes it, thus leaving a pattern of the charged areas which is a reproduction of the image desired.
  • the charged area attracts a powdered or other usually particulated imageforming material which may be fused or otherwise treated to make the image permanent.
  • Other processes differ in that the image is created by electrical dissipation of the static charge in nonimage areas; in this and other processes (see Vaurio and Fird, supra), the common characteristic is an electrically conductive base paper.
  • the preferred homopolymer of the described class is derived from free radical polymerization of dimethyl diallyl ammonium chloride.
  • the polymerization method described by Butler and Angelo, Journal of American Chemical Society, vol. 79, p. 3128 (1957), may be used satisfactorily to make polymers which perform in our invention.
  • Also useful is the homopolymer of the monomer diallyl methyl fi-propionamido ammonium chloride.
  • Other polymers useful in our invention are included in the'decription of Butlers US. Pat. 3,288,770.
  • Diallyl ammonium monomers undergo cyclization during free radical polymerization to form piperidinium rings.
  • the homopolymer of dimethyl diallyl ammonium chloride may be described as a poly dimethyl-3,5-methylene piperidinium salt.
  • the homopolymer of diallyl methyl B-propionamido ammonium chloride, for example, is known as poly [N-methyl-N-(fi-propionamido) 3,5-methylene piperidinium chloride].
  • polymers containing repeating groups of Formula I may be derived from polymerization of monomers of the formula where R is an alkyl group of one to eighteen carbon atoms, R is selected from the group consisting of R and p-proprionamido, and A" is an anion.
  • Anions which are particularly of interest are fluoride, chloride, bromide, hydroxide, nitrate, acetate, HSO,- and H2PO4
  • Water-soluble copolymers and more complex polymers of the above-described monomers containing at least about 90% of Formula I repeating groups are contemplated within the scope of our invention. Any copolymerizable monomer which will form a water-soluble polymer CHFC or, after polymerization, as
  • R represents a member of the class consisting of hydrogen, halogen, R and alkyl groups of 1 to 4 carbon atoms
  • R represents a radical of the class consisting of aryl and alkaryl radicals and radicals represented by the formulas where R and R each represents a radical selected from the class consisting of alkyl, cycloalkyl, and alkoxyalkyl radicals, R; has the same meaning as R and R and, in addition, an aryl radical, R and R each represents a member of the class consisting of hydrogen, and alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and alkoxyalkyl radicals, and R has the same meaning as R nd R See Schuller and Thomas US.
  • diallyl amine monomers which are preferably copolymerized in the form of a hydrohalide salt. See Butler, Angelo, and Cranshaw, US. Pat. 2,926,- 161. They may be described in terms of the formula where R is an alkyl group of 1 to 4 carbon atoms or B- propionamido, and A- is a halide anion.
  • Also contemplated in our invention is the use in paper of the above-described homopolymers and copolymers having included in their polymerized structures certain compatible polyethylenic unsaturated compounds.
  • Such polyethylenic unsaturated compounds when present in small amounts (i.e., up to about 10%) during the polymerization of a dialkyl diallyl ammonium halide monomer, cause the resulting polymer to be highly branched and/ or cross-linked.
  • the branched polymer also imparts superior barrier properties to the paper substrate preventing solvent from the application of the photoconductive upper layer from diffusing into the paper.
  • the preferred branching agents are methylene bisacrylamide, triallyl amine hydrohalide salts, triallyl quaternary ammonium salts having as a fourth group an alkyl group of 1 to 4 carbon atoms, and tetraallyl ammonium salts.
  • Polyallyl sucrose and other allyl substituted polyalcohols may be used, as well as polyallyl polyamine hydrohalides and quaternary salts.
  • the amount of each of these branching agents required to get the desired results varies with each compound, the only requirement being that irreversible (water-insoluble) gel formation should be avoided. As little as 0.001% of such branching agent will significantly improve the film forming ability of the polymer. Preferred ranges are between about 0.01 percent and 0.1 percent.
  • Example I A 4% by weight aqueous solution of a copolymer of dimethyl diallyl ammonium chloride and methyl dodecyl diallyl ammonium chloride in the molar ratio of 17.5 to 1 was applied to Bergstrom Paper Companys Indsen #1 raw coating stock (basis weight 46 lbs. per 3,300 square feet) using a 3 mil, wire-wound Meyer rod. This rod applies approximately 0.3 lb. of pure polymer per 3,000 square feet of paper. The sample was then dried in an oven at 105 C. for 20 to 30 minutes. An 8 square inch circular sample was cut and placed into a constant conditions room for 16 hours at 50% relative humidity and 72 F. After this period, the sample was conditioned for 72 hours at 23 relative humidity.
  • Example H 20 45 80 Rel. Humidity 10g X 107 x Using the same polymer in a concentration of three pounds faer 31,000 sq. ft., the following surface resistances were oun O Hlllmdlliy 8 Example III In another test in which two pounds of our preferred homopolymer was spread on 3,000 sq. ft. of paper, the conductivity results, measured in terms of surface resistance, were virtually identical to a polymer disclosed in US. Pat. 3,011,918. There were no objectionable odor or background discoloration in the paper treated with the polymers of our invention.
  • Example IV A 4% by weight aqueous solution of poly (methyl propionamido diallyl ammonium chloride) was applied to the test paper as above. After treatment as in Example I, this paper gave a surface resistivity value of 2.0x 10
  • Example V A 4% by weight solution of a copolymer of dimethyl diallyl ammonium chloride (93% by weight) acrylamide (4%) and acryonitrile (3%) was applied and treated as in Example I. At a relative humidity of 12%, the surface resistivity was 8.6X10
  • Example VI A 4% by weight solution of a copolymer of dimethyl diallyl ammonium chloride (96% by weight) and acrylonitrile (4%) was applied and treated as in Example I. At a relative humidity of 16%, the surface resistivity was 1.8 X 10
  • Example VII A 4% by weight solution of a copolymer of dimethyl diallyl ammonium chloride (95% by weight) and diacetone acrylamide 5% was applied and treated as in Example I. The surface resistivity at 24% relative humidity was 3.6X
  • Example VIII A 4% solution of homopolymer of diethyl allyl ammonium chloride was applied and treated as in Example I.
  • the surface resistivity at relative humidity was 7.9 10
  • Example IX A 4% by weight solution of a copolymer of dimethyl diallyl ammonium chloride copolymerized with 0.03 weight percent methylene bisacrylamide was applied and treated as in Example I. The surface resistivity at 23% relatively humidity was 1.8 x10
  • Example X A 4% solution of dimethyl diallyl ammonium copolymerized with 0.12 weight percent tetraallyl ammonium chloride was applied and treated as in Example I. The surface resistivity at 23% relative humidity was l.4 10
  • Solutions of our polymers may be applied to paper or cellulosic Webs by coating, diping, brushing, Wet end addition, etc. Concentrations of the polymer may vary widely to fit the method of handling. Generally about 0.5-3.0 pounds of polymer should be applied per 3,000 sq. ft. but for some purposes as little as 0.1 pound will provide sufiicient conductivity. The upper limit of addition will be determined largely by economics; so far as we are aware, there is no upper limit which is or will be detrimental to the electroconductive character of the paper.
  • Electroconductive paper including a layer of poly- [N-methyl-N-(fi-propionamido)-3,5-methylene piperidinium chloride].
  • Electroconductive paper including a layer of poly- (N,N-dimethyl-3,5-methylene piperidinium chloride).
  • Electroconductive paper including a layer of poly- (N,N dimethyl 3,5 methylene piperidinium chloride) crosslinked with from about 0.1% to about 1% methylenebisacrylamide, based on the weight of the polymer.
  • Electroconductive paper containing about 0.1 to about 3.0 pounds per 3000 square feet of at least one water-soluble polymer comprising at least by weight groups of the formula l CH2 where R is an alkyl group containing one to eighteen carbon atoms, R is selected from the group consisting of R and where R represents a member of the class consisting of hydrogen, halogen, and alkyl groups of 1 to 4 carbon atoms, and R represents a radical of the class consisting of aryl and alkaryl radicals and radicals represented by the formulas where R and R each represents a radical selected from the class consisting of alkyl, cycloalkyl, and alkoxyalkyl radicals, R has the same meaning as R and R and, in addition, an aryl radical, R and R each represents a member of the class consisting of hydrogen, and alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and alkoxyalkyl radicals and R has the same meaning as R and R 7. Paper of
  • paper of claim 8 in which the water soluble polyethylenically unsaturated monomer is selected from the group consisting of methylene bisacrylamide, triallyl amine hydrohalide salts, tetrallyl ammonium salts, and triallyl ammonium salts including an alkyl group of 1 to 4 carbon atoms.
  • Electroconductive paper containing at least about 0.1 pound per 3000 square feet of at least one watersoluble polymer consisting essentially of units derived from monomers of the formula CH2 (l'llHn CH2 CH:
  • R is an alkyl group of 1 to 18 carbon atoms and R is selected from the group consisting of R and 11. Paper of claim in which the polymer consists essentially of units derived from dimethyl diallyl ammonium chloride.
  • Electroconductive paper containing at least about 0.1 pound per 3000 square feet of at least one watersoluble polymer derived from polymerization of a monomer mix of (a) monomers of the formula where 'R is an alkyl group of 1 to 18 carbon atoms, R is selected from the group consisting of R and f1- propionamido, and (b) up to about 10% by weight of a water-soluble copolymerizable branching agent.
  • Paper of claim 12 in which the branching agent is selected from the group consisting of polyallyl substituted polyalcohols, polyallyl substituted polyamine hydrohalides and quaternary salts, and N,N-methylene bisacrylamide.
  • Method of making electroconductive paper comprising incorporating therein at least about 0.1 pound per 3,000 square feet of a water-soluble polymer consisting. essentially of repeating units derived from dimethyl diallyl ammonium chloride.
  • Method of making electroconductive paper com- 8 prising incorporating in said paper about 0.1 to about 3.0 pounds, per 3,000 square feet of paper, of watersoluble polymer comprising at least by weight groups of the formula 2 a R Rl where R is an alkyl group of 1 to 18 carbon atoms and R is selected from the group consisting of R and 16.
  • Method of claim 15 in which the polymer is a homopolymer of dimethyl diallyl ammonium chloride and is incorporated to the extent of at least 0.5 pound per 3,000 square feet of paper.
  • Method of claim 15 in which a solution of polymer is formed into a layer on the paper and subsequently dried.

Description

United States Patent 3,544,318 ELECTROCONDUCTIVE PAPER Jerry E. Boothe, Pittsburgh, and Merwiu Frederick Hoover, Bethel Park, Pa., assignors to Calgon Corporation, Pittsburgh, Pa.
No Drawing. Continuation-impart of application Ser. No. 462,742, June 9, 1965. This application July 10, 1968, Ser. No. 743,634
Int. Cl, G03g 7/00; B44d N00 US. Cl. 96-15 20 Claims ABSTRACT OF THE DISCLOSURE Electrocondnctive paper useful typically in making copies by an electrostatic process is made by incorporating therein a polymer comprising at least 90% monomers of the formula (CHFCHCHa)2 i i A where R is an alkyl group of 1 to 18 carbon atoms and -R is R or B-propionamido and A is an anion.
RELATED APPLICATION This is a continuation-in-part of our copending application S.N. 462,742 filed June 9, 1965 now abandoned.
BACKGROUND OF THE INVENTION This invention relates to paper containing electroconductive materials. In particular, it relates to paper rendered electroconductive by a layer or coating of electroconductive material, which paper is useful in various copying processes and devices.
Electroconductive paper may be used to distribute electrical stresses in various insulating products; see US. Pat. 3,148,107. Where electrically conductive paper is to be used for nonimpact printing, a substrate, backing, impregnation coating, or layer of electrically conductive material is usually constructed. See Vaurio and Fird, Electrically Conductive Paper for Nonimpact Printing, Tappi, December 1964, vol. 47, No. 12, pp. 163A-165A. Various types of nonimpact printing processes are known as electrostatographic, electrophotographic, electrographic, Electrofax, and other processes. As a rule such processes call for the placement of an electric charge on the paper, which may be accomplished by a corona discharge, for example. The charge is, in most such processes, placed on the paper in darkness. The paper may also contain a photo-responsive or photo-conductive layer or material, now popularly a specially treated zinc oxide, which causes the charge to be dissipated in an area where light strikes it, thus leaving a pattern of the charged areas which is a reproduction of the image desired. The charged area attracts a powdered or other usually particulated imageforming material which may be fused or otherwise treated to make the image permanent. Other processes differ in that the image is created by electrical dissipation of the static charge in nonimage areas; in this and other processes (see Vaurio and Fird, supra), the common characteristic is an electrically conductive base paper.
Probably the most common system at present is the direct electrostatic process; see Chemical & Engineering News, July 20, 1964, pp. 88-89; US. Pat. 3,052,539. This process is similar to the xerographic method of copy reproduction; however, the conductive substrate is built into paper rather than being on a separate drum or other device.
Among the desirable characteristics of an electrically conductive material for use in nonimpact printing are 3,544,318 Patented Dec. 1, 1970 Our invention is useful in imparting electroconductive characteristics to the paper for use in such processes as the above.
We have discovered that the class of water-soluble polymers containing at least about repeating groups of the formula where R is an alkyl group containing one to eighteen carbon atoms, R is selected from the group consisting of R and and A is an anion, may be used in making electroconductive paper. Any water-soluble polymer of this description is within the scope of our invention.
The preferred homopolymer of the described class is derived from free radical polymerization of dimethyl diallyl ammonium chloride. The polymerization method described by Butler and Angelo, Journal of American Chemical Society, vol. 79, p. 3128 (1957), may be used satisfactorily to make polymers which perform in our invention. Also useful is the homopolymer of the monomer diallyl methyl fi-propionamido ammonium chloride. Other polymers useful in our invention are included in the'decription of Butlers US. Pat. 3,288,770.
Diallyl ammonium monomers undergo cyclization during free radical polymerization to form piperidinium rings. The homopolymer of dimethyl diallyl ammonium chloride may be described as a poly dimethyl-3,5-methylene piperidinium salt. The homopolymer of diallyl methyl B-propionamido ammonium chloride, for example, is known as poly [N-methyl-N-(fi-propionamido) 3,5-methylene piperidinium chloride].
Thus, polymers containing repeating groups of Formula I may be derived from polymerization of monomers of the formula where R is an alkyl group of one to eighteen carbon atoms, R is selected from the group consisting of R and p-proprionamido, and A" is an anion.
Anions which are particularly of interest are fluoride, chloride, bromide, hydroxide, nitrate, acetate, HSO,- and H2PO4 Water-soluble copolymers and more complex polymers of the above-described monomers containing at least about 90% of Formula I repeating groups are contemplated within the scope of our invention. Any copolymerizable monomer which will form a water-soluble polymer CHFC or, after polymerization, as
GHe-C where R represents a member of the class consisting of hydrogen, halogen, R and alkyl groups of 1 to 4 carbon atoms, and R represents a radical of the class consisting of aryl and alkaryl radicals and radicals represented by the formulas where R and R each represents a radical selected from the class consisting of alkyl, cycloalkyl, and alkoxyalkyl radicals, R; has the same meaning as R and R and, in addition, an aryl radical, R and R each represents a member of the class consisting of hydrogen, and alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and alkoxyalkyl radicals, and R has the same meaning as R nd R See Schuller and Thomas US. Pat. 2,923,701 for a description of the mechanism of copolymerization of such monomers with the diallyl quaternary ammonium compounds discussed above. See also Schuller et al., Journal of Chemical & Engineering Data, vol. 4, p. 273 (1959).
We may also use diallyl amine monomers which are preferably copolymerized in the form of a hydrohalide salt. See Butler, Angelo, and Cranshaw, US. Pat. 2,926,- 161. They may be described in terms of the formula where R is an alkyl group of 1 to 4 carbon atoms or B- propionamido, and A- is a halide anion.
Also contemplated in our invention is the use in paper of the above-described homopolymers and copolymers having included in their polymerized structures certain compatible polyethylenic unsaturated compounds. Such polyethylenic unsaturated compounds, when present in small amounts (i.e., up to about 10%) during the polymerization of a dialkyl diallyl ammonium halide monomer, cause the resulting polymer to be highly branched and/ or cross-linked. The branched polymer also imparts superior barrier properties to the paper substrate preventing solvent from the application of the photoconductive upper layer from diffusing into the paper. The preferred branching agents are methylene bisacrylamide, triallyl amine hydrohalide salts, triallyl quaternary ammonium salts having as a fourth group an alkyl group of 1 to 4 carbon atoms, and tetraallyl ammonium salts. However, we may use any water soluble, polyunsaturated compound which is copolymerizable with the diallyl monomers previously described. Polyallyl sucrose and other allyl substituted polyalcohols may be used, as well as polyallyl polyamine hydrohalides and quaternary salts. The amount of each of these branching agents required to get the desired results varies with each compound, the only requirement being that irreversible (water-insoluble) gel formation should be avoided. As little as 0.001% of such branching agent will significantly improve the film forming ability of the polymer. Preferred ranges are between about 0.01 percent and 0.1 percent.
As is known in the art of electrostatic printing and other forms of nonimpact printing, conductivity measurements for conductive coatings on paper may be made on the conductive areas only; that is, the electrodes of the conductivity device may be simply attached to the conductive surface of the paper. Generally speaking, papers adapted for use in various types of nonimpact printing may have surface resistivities in the range of about 2.5 10 to about 3.0 10 Molecular Weights of our polymers are apparently not critical to conductivity.
The following examples illustrate not only the utility of our invention in electroconductive paper, but also the conductivity of the paper at various relative humidities. The indicated changes in conductivity with relative humidity are comparatively excellent in the present state of the art.
Example I I A 4% by weight aqueous solution of a copolymer of dimethyl diallyl ammonium chloride and methyl dodecyl diallyl ammonium chloride in the molar ratio of 17.5 to 1 was applied to Bergstrom Paper Companys Indsen #1 raw coating stock (basis weight 46 lbs. per 3,300 square feet) using a 3 mil, wire-wound Meyer rod. This rod applies approximately 0.3 lb. of pure polymer per 3,000 square feet of paper. The sample Was then dried in an oven at 105 C. for 20 to 30 minutes. An 8 square inch circular sample was cut and placed into a constant conditions room for 16 hours at 50% relative humidity and 72 F. After this period, the sample was conditioned for 72 hours at 23 relative humidity. Current measurements were made after applying v. DC using Keithley equipment consisting of a Model No. 240 Regulated High Voltage Supply, a Model No. 6105 Resistivity Adapter and a Model 610-B Electrometer. The resistivity adapter is suitable for determining both surface and volume resistivities. Electrodes are constructed of stainless steel; however, for measurements at relative humidities of greater than 70% a special graphite center electrode was used. Current readings were converted to obtain resistivity values. The surface resistivity of this polymer was 5.9X10 ohms/square.
Example H 20 45 80 Rel. Humidity 10g X 107 x Using the same polymer in a concentration of three pounds faer 31,000 sq. ft., the following surface resistances were oun O Hlllmdlliy 8 Example III In another test in which two pounds of our preferred homopolymer was spread on 3,000 sq. ft. of paper, the conductivity results, measured in terms of surface resistance, were virtually identical to a polymer disclosed in US. Pat. 3,011,918. There were no objectionable odor or background discoloration in the paper treated with the polymers of our invention.
Example IV A 4% by weight aqueous solution of poly (methyl propionamido diallyl ammonium chloride) was applied to the test paper as above. After treatment as in Example I, this paper gave a surface resistivity value of 2.0x 10 Example V A 4% by weight solution of a copolymer of dimethyl diallyl ammonium chloride (93% by weight) acrylamide (4%) and acryonitrile (3%) was applied and treated as in Example I. At a relative humidity of 12%, the surface resistivity was 8.6X10
Example VI A 4% by weight solution of a copolymer of dimethyl diallyl ammonium chloride (96% by weight) and acrylonitrile (4%) was applied and treated as in Example I. At a relative humidity of 16%, the surface resistivity was 1.8 X 10 Example VII A 4% by weight solution of a copolymer of dimethyl diallyl ammonium chloride (95% by weight) and diacetone acrylamide 5% was applied and treated as in Example I. The surface resistivity at 24% relative humidity was 3.6X
Example VIII A 4% solution of homopolymer of diethyl allyl ammonium chloride was applied and treated as in Example I. The surface resistivity at relative humidity was 7.9 10
Example IX A 4% by weight solution of a copolymer of dimethyl diallyl ammonium chloride copolymerized with 0.03 weight percent methylene bisacrylamide was applied and treated as in Example I. The surface resistivity at 23% relatively humidity was 1.8 x10 Example X A 4% solution of dimethyl diallyl ammonium copolymerized with 0.12 weight percent tetraallyl ammonium chloride was applied and treated as in Example I. The surface resistivity at 23% relative humidity was l.4 10
Solutions of our polymers may be applied to paper or cellulosic Webs by coating, diping, brushing, Wet end addition, etc. Concentrations of the polymer may vary widely to fit the method of handling. Generally about 0.5-3.0 pounds of polymer should be applied per 3,000 sq. ft. but for some purposes as little as 0.1 pound will provide sufiicient conductivity. The upper limit of addition will be determined largely by economics; so far as we are aware, there is no upper limit which is or will be detrimental to the electroconductive character of the paper.
We do not intend to be limited to the specific examples and illustrations employed in the preceding description of our invention. It may be otherwise variously practiced within the scope of the following claims.
We claim:
1. Electroconductive paper including a layer of poly- [N-methyl-N-(fi-propionamido)-3,5-methylene piperidinium chloride].
2. Electroconductive paper including a layer of poly- (N,N-dimethyl-3,5-methylene piperidinium chloride).
3. Electroconductive paper including a layer of poly- (N,N dimethyl 3,5 methylene piperidinium chloride) crosslinked with from about 0.1% to about 1% methylenebisacrylamide, based on the weight of the polymer.
4. Electroconductive paper containing about 0.1 to about 3.0 pounds per 3000 square feet of at least one water-soluble polymer comprising at least by weight groups of the formula l CH2 where R is an alkyl group containing one to eighteen carbon atoms, R is selected from the group consisting of R and where R represents a member of the class consisting of hydrogen, halogen, and alkyl groups of 1 to 4 carbon atoms, and R represents a radical of the class consisting of aryl and alkaryl radicals and radicals represented by the formulas where R and R each represents a radical selected from the class consisting of alkyl, cycloalkyl, and alkoxyalkyl radicals, R has the same meaning as R and R and, in addition, an aryl radical, R and R each represents a member of the class consisting of hydrogen, and alkyl, cycloalkyl, aryl, alkaryl, aralkyl, and alkoxyalkyl radicals and R has the same meaning as R and R 7. Paper of claim 4 in which the polymer includes up to about 10% by weight units derived from the group consisting of acrylamide, diacetone acrylamide, N-methylolacrylamide, and N-vinyl 2-pyrrolidinone.
8. Paper of claim 4 in which the polymer includes up to about 10 weight percent of a Water soluble polyethylenically unsaturated monomer branching agent.
9. Paper of claim 8 in which the water soluble polyethylenically unsaturated monomer is selected from the group consisting of methylene bisacrylamide, triallyl amine hydrohalide salts, tetrallyl ammonium salts, and triallyl ammonium salts including an alkyl group of 1 to 4 carbon atoms.
10. Electroconductive paper containing at least about 0.1 pound per 3000 square feet of at least one watersoluble polymer consisting essentially of units derived from monomers of the formula CH2 (l'llHn CH2 CH:
where R is an alkyl group of 1 to 18 carbon atoms and R is selected from the group consisting of R and 11. Paper of claim in which the polymer consists essentially of units derived from dimethyl diallyl ammonium chloride.
12. Electroconductive paper containing at least about 0.1 pound per 3000 square feet of at least one watersoluble polymer derived from polymerization of a monomer mix of (a) monomers of the formula where 'R is an alkyl group of 1 to 18 carbon atoms, R is selected from the group consisting of R and f1- propionamido, and (b) up to about 10% by weight of a water-soluble copolymerizable branching agent.
13. Paper of claim 12 in which the branching agent is selected from the group consisting of polyallyl substituted polyalcohols, polyallyl substituted polyamine hydrohalides and quaternary salts, and N,N-methylene bisacrylamide. i
14. Method of making electroconductive paper comprising incorporating therein at least about 0.1 pound per 3,000 square feet of a water-soluble polymer consisting. essentially of repeating units derived from dimethyl diallyl ammonium chloride.
15. Method of making electroconductive paper com- 8 prising incorporating in said paper about 0.1 to about 3.0 pounds, per 3,000 square feet of paper, of watersoluble polymer comprising at least by weight groups of the formula 2 a R Rl where R is an alkyl group of 1 to 18 carbon atoms and R is selected from the group consisting of R and 16. Method of claim 15 in which the polymer contains a cross-linking agent.
17. Method of claim 15 in which the polymer contains a branching agent.
18. Method of claim 15 in which the polymer is a homopolymer of dimethyl diallyl ammonium chloride and is incorporated to the extent of at least 0.5 pound per 3,000 square feet of paper.
19. Method of claim 15 in which the polymer is added to the paper in the form of an aqueous solution.
20. Method of claim 15 in which a solution of polymer is formed into a layer on the paper and subsequently dried.
References Cited UNITED STATES PATENTS 2,926,161 2/1960 Butler et al.' 26089.7 3,216,853 11/1965 Gess 117-201 WILLIAM L. JARVIS, Primary Examiner US. Cl. X.R.
Patent No. 3,544,318 Dated December 1, 1970 lnventofls) Jerry E. Boothe et a1 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 2 line 7 after "tastes" insert and Column line 36, "allyl" should read diallyl line 46, "relatively" should read relative line 54 "diping" should read dipping Signed and sealed this 27th day of April 1971 (SEAL) Attest:
EDWARD M.FLETCHER,JR. WILLIAM E. SCHUYLER, Attesting Officer Commissioner of Pater FOBM PO-HJSO (10-69) UscMM Dc
US743634A 1965-06-09 1968-07-10 Electroconductive paper Expired - Lifetime US3544318A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US46274265A 1965-06-09 1965-06-09
US74363468A 1968-07-10 1968-07-10

Publications (1)

Publication Number Publication Date
US3544318A true US3544318A (en) 1970-12-01

Family

ID=27040434

Family Applications (1)

Application Number Title Priority Date Filing Date
US743634A Expired - Lifetime US3544318A (en) 1965-06-09 1968-07-10 Electroconductive paper

Country Status (3)

Country Link
US (1) US3544318A (en)
FR (1) FR2012630A6 (en)
NL (1) NL149917B (en)

Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3652268A (en) * 1970-03-16 1972-03-28 Dick Co Ab Barrier coated electrophotographic sheet suitable for liquid development
US3720514A (en) * 1969-07-17 1973-03-13 Xerox Corp Electrophotographic paper having an inorganic colloidal oxide coating
US3787235A (en) * 1970-07-06 1974-01-22 Xerox Corp Method of electrophotographic sensitive paper
US3804668A (en) * 1972-03-30 1974-04-16 Rohm & Haas Electroconductive paper
US3830655A (en) * 1971-05-19 1974-08-20 Allied Colloids Mfg Conductive papers
US3862091A (en) * 1972-03-07 1975-01-21 Gaf Corp Quaternized n-vinyl lactam polymeric compositions and mannich adducts thereof
US3870559A (en) * 1970-02-25 1975-03-11 Ici Ltd Paper treatment
US3887496A (en) * 1972-08-02 1975-06-03 Dow Chemical Co Quaternary ammonium electroconductive resin coating compositions
US3950169A (en) * 1972-01-17 1976-04-13 Agfa-Gevaert N.V. Electrophotographic element with polymeric conductive layer
US3986873A (en) * 1972-11-16 1976-10-19 Ekaterina Egorovna Sirotkina Photosensitive polymeric materials comprising poly-n-vinylphenoxazine and poly-n-vinylphenothiazine
US3991256A (en) * 1972-08-02 1976-11-09 The Dow Chemical Company Preparing electrostatographic printing sheet, article thereof and article coated with quaternary ammonium electroconductive resin
US4011080A (en) * 1974-03-01 1977-03-08 Eastman Kodak Company Electrophotographic elements comprising polysilicic acid-crosslinked conductive polymers
US4037017A (en) * 1975-12-08 1977-07-19 Hercules Incorporated Electroconductive paper
US4040984A (en) * 1975-05-12 1977-08-09 Calgon Corporation Electroconductive polysalt complexes
US4061833A (en) * 1973-11-14 1977-12-06 The Dow Chemical Company Latex coatings for electrographic sheets
US4081419A (en) * 1975-06-12 1978-03-28 Toyo Soda Manufacturing Co., Ltd. Process for producing a polymer emulsion
US4151202A (en) * 1976-03-01 1979-04-24 Nalco Chemical Company Preparation of diallyl dimethyl ammonium chloride and polydiallyl dimethyl ammonium chloride
US4171417A (en) * 1978-10-30 1979-10-16 Calgon Corporation Polymers with improved solvent holdout in electroconductive paper
US4222901A (en) * 1978-11-15 1980-09-16 Calgon Corporation Electroconductive polymers having improved solvent holdout properties
US4282118A (en) * 1978-11-15 1981-08-04 Calgon Corporation Electroconductive polymer composition
US4287172A (en) * 1977-09-23 1981-09-01 L'oreal Cosmetic compositions for the hair and the skin, based on polymers which contain amino groups and recurring units having a cyclic structure
US4306996A (en) * 1980-05-05 1981-12-22 Calgon Corporation Electroconductive polymer composition
US4554181A (en) * 1984-05-07 1985-11-19 The Mead Corporation Ink jet recording sheet having a bicomponent cationic recording surface
DE3716356A1 (en) * 1986-05-15 1987-11-19 Dai Ichi Kogyo Seiyaku Co Ltd COMPOSITION FOR FORMING CONDUCTIVE FILMS
US4713431A (en) * 1985-10-21 1987-12-15 Nalco Chemical Company High molecular weight DADMAC polymers by inverse emulsion technology
US4927896A (en) * 1986-04-25 1990-05-22 Ethyl Corporation Process for polymerizing monoallylamine
US5973108A (en) * 1997-05-12 1999-10-26 Clariant Gmbh Unsaturated polycations and their preparation and use
US6074761A (en) * 1997-06-13 2000-06-13 Ppg Industries Ohio, Inc. Inkjet printing media
US6323306B1 (en) 1998-09-08 2001-11-27 Ciba Specialty Chemicals Water Treatments Ltd. Preparation of water-soluble cross-linked cationic polymers
DE10214087A1 (en) * 2002-03-28 2003-10-23 Fraunhofer Ges Forschung Water soluble branched block copolymers
US20040034156A1 (en) * 2002-08-15 2004-02-19 Zhiqiang Song High molecular weight cationic polymers obtained by post-polymerization crosslinking reaction
US20040226676A1 (en) * 2003-05-13 2004-11-18 Zhiqiang Song Use of water-soluble crosslinked cationic polymers for controlling deposition of pitch and stickies in papermaking
US20050182222A1 (en) * 2002-03-01 2005-08-18 Werner Jaeger Water soluble branched block copolymers
US20070238842A1 (en) * 2002-08-15 2007-10-11 Zhiqiang Song High molecular weight cationic polymers obtained by post-polymerization crosslinking reaction
WO2014074397A1 (en) 2012-11-07 2014-05-15 Bayer Materialscience Llc Process for incorporating an ion-conducting polymer into a polymeric article to achieve anti-static behavior

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2926161A (en) * 1958-03-10 1960-02-23 Peninsular Chem Res Inc Linear homopolymers of diallyl amines
US3216853A (en) * 1960-09-06 1965-11-09 Scott Paper Co Electrostatic conductive paper and process of manufacture thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2926161A (en) * 1958-03-10 1960-02-23 Peninsular Chem Res Inc Linear homopolymers of diallyl amines
US3216853A (en) * 1960-09-06 1965-11-09 Scott Paper Co Electrostatic conductive paper and process of manufacture thereof

Cited By (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3720514A (en) * 1969-07-17 1973-03-13 Xerox Corp Electrophotographic paper having an inorganic colloidal oxide coating
US3870559A (en) * 1970-02-25 1975-03-11 Ici Ltd Paper treatment
US3652268A (en) * 1970-03-16 1972-03-28 Dick Co Ab Barrier coated electrophotographic sheet suitable for liquid development
US3787235A (en) * 1970-07-06 1974-01-22 Xerox Corp Method of electrophotographic sensitive paper
US3830655A (en) * 1971-05-19 1974-08-20 Allied Colloids Mfg Conductive papers
US3950169A (en) * 1972-01-17 1976-04-13 Agfa-Gevaert N.V. Electrophotographic element with polymeric conductive layer
US3862091A (en) * 1972-03-07 1975-01-21 Gaf Corp Quaternized n-vinyl lactam polymeric compositions and mannich adducts thereof
US3804668A (en) * 1972-03-30 1974-04-16 Rohm & Haas Electroconductive paper
US3887496A (en) * 1972-08-02 1975-06-03 Dow Chemical Co Quaternary ammonium electroconductive resin coating compositions
US3991256A (en) * 1972-08-02 1976-11-09 The Dow Chemical Company Preparing electrostatographic printing sheet, article thereof and article coated with quaternary ammonium electroconductive resin
US3986873A (en) * 1972-11-16 1976-10-19 Ekaterina Egorovna Sirotkina Photosensitive polymeric materials comprising poly-n-vinylphenoxazine and poly-n-vinylphenothiazine
US4061833A (en) * 1973-11-14 1977-12-06 The Dow Chemical Company Latex coatings for electrographic sheets
US4011080A (en) * 1974-03-01 1977-03-08 Eastman Kodak Company Electrophotographic elements comprising polysilicic acid-crosslinked conductive polymers
US4040984A (en) * 1975-05-12 1977-08-09 Calgon Corporation Electroconductive polysalt complexes
US4081419A (en) * 1975-06-12 1978-03-28 Toyo Soda Manufacturing Co., Ltd. Process for producing a polymer emulsion
US4037017A (en) * 1975-12-08 1977-07-19 Hercules Incorporated Electroconductive paper
US4151202A (en) * 1976-03-01 1979-04-24 Nalco Chemical Company Preparation of diallyl dimethyl ammonium chloride and polydiallyl dimethyl ammonium chloride
US4426375A (en) 1977-09-23 1984-01-17 L'oreal Cosmetic compositions for the hair and the skin based on polymers which contain amino groups and recurring units having a cyclic structure
US4287172A (en) * 1977-09-23 1981-09-01 L'oreal Cosmetic compositions for the hair and the skin, based on polymers which contain amino groups and recurring units having a cyclic structure
US4171417A (en) * 1978-10-30 1979-10-16 Calgon Corporation Polymers with improved solvent holdout in electroconductive paper
US4282118A (en) * 1978-11-15 1981-08-04 Calgon Corporation Electroconductive polymer composition
US4222901A (en) * 1978-11-15 1980-09-16 Calgon Corporation Electroconductive polymers having improved solvent holdout properties
US4306996A (en) * 1980-05-05 1981-12-22 Calgon Corporation Electroconductive polymer composition
US4554181A (en) * 1984-05-07 1985-11-19 The Mead Corporation Ink jet recording sheet having a bicomponent cationic recording surface
US4713431A (en) * 1985-10-21 1987-12-15 Nalco Chemical Company High molecular weight DADMAC polymers by inverse emulsion technology
US4927896A (en) * 1986-04-25 1990-05-22 Ethyl Corporation Process for polymerizing monoallylamine
DE3716356A1 (en) * 1986-05-15 1987-11-19 Dai Ichi Kogyo Seiyaku Co Ltd COMPOSITION FOR FORMING CONDUCTIVE FILMS
US5973108A (en) * 1997-05-12 1999-10-26 Clariant Gmbh Unsaturated polycations and their preparation and use
US6074761A (en) * 1997-06-13 2000-06-13 Ppg Industries Ohio, Inc. Inkjet printing media
US6340725B1 (en) 1997-06-13 2002-01-22 Hewlett-Packard Company Inkjet printing media
US6323306B1 (en) 1998-09-08 2001-11-27 Ciba Specialty Chemicals Water Treatments Ltd. Preparation of water-soluble cross-linked cationic polymers
US20050182222A1 (en) * 2002-03-01 2005-08-18 Werner Jaeger Water soluble branched block copolymers
DE10214087A1 (en) * 2002-03-28 2003-10-23 Fraunhofer Ges Forschung Water soluble branched block copolymers
DE10214087B4 (en) * 2002-03-28 2004-05-06 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Water soluble branched block copolymers
US20040034156A1 (en) * 2002-08-15 2004-02-19 Zhiqiang Song High molecular weight cationic polymers obtained by post-polymerization crosslinking reaction
US20050261419A1 (en) * 2002-08-15 2005-11-24 Zhiqiang Song High molecular weight cationic polymers obtained by post-polymerization crosslinking reaction
US7205369B2 (en) 2002-08-15 2007-04-17 Ciba Specialty Chemicals Water Treatments Ltd. High molecular weight cationic polymers obtained by post-polymerization crosslinking reaction
US7238752B2 (en) 2002-08-15 2007-07-03 Ciba Specialty Chemicals Water Treatments Ltd. High molecular weight cationic polymers obtained by post-polymerization crosslinking reaction
US20070238842A1 (en) * 2002-08-15 2007-10-11 Zhiqiang Song High molecular weight cationic polymers obtained by post-polymerization crosslinking reaction
US7425597B2 (en) 2002-08-15 2008-09-16 Ciba Specialty Chemicals Water Treatments Ltd. High molecular weight cationic polymers obtained by post-polymerization crosslinking reaction
US20040226676A1 (en) * 2003-05-13 2004-11-18 Zhiqiang Song Use of water-soluble crosslinked cationic polymers for controlling deposition of pitch and stickies in papermaking
US7407561B2 (en) 2003-05-13 2008-08-05 Ciba Specialty Chemicals Water Treatments Ltd. Use of water-soluble crosslinked cationic polymers for controlling deposition of pitch and stickies in papermaking
WO2014074397A1 (en) 2012-11-07 2014-05-15 Bayer Materialscience Llc Process for incorporating an ion-conducting polymer into a polymeric article to achieve anti-static behavior
US8758860B1 (en) * 2012-11-07 2014-06-24 Bayer Materialscience Llc Process for incorporating an ion-conducting polymer into a polymeric article to achieve anti-static behavior
CN105026469A (en) * 2012-11-07 2015-11-04 拜尔材料科学有限公司 Process for incorporating an ion-conducting polymer into a polymeric article to achieve anti-static behavior
EP2917269A4 (en) * 2012-11-07 2016-06-22 Covestro Llc Process for incorporating an ion-conducting polymer into a polymeric article to achieve anti-static behavior
CN105026469B (en) * 2012-11-07 2017-11-24 拜尔材料科学有限公司 Ion-conducting polymers are attached in polymer product to realize the method for antistatic behaviour

Also Published As

Publication number Publication date
NL6607718A (en) 1966-12-12
FR2012630A6 (en) 1970-03-20
NL149917B (en) 1976-06-15

Similar Documents

Publication Publication Date Title
US3544318A (en) Electroconductive paper
USRE28543E (en) Electroconductive paper
US3689468A (en) Unsaturated quaternary monomers and polymers
US3486932A (en) Electroconductive paper
CA1147096A (en) Protective overcoats for electrophotographic elements
US3702799A (en) Polymers of quaternary ammonium compounds used as wet strength agents in paper
US3745005A (en) Electrophotographic elements having barrier layers
AU606625B2 (en) Aqueous dispersion of cationic polymer
US3110621A (en) Electrostatic recording paper
GB1586198A (en) Transfer sheet and process for preparation thereof
CA1168431A (en) Electroconductive polymer composition
US3798032A (en) Electroconductive coating, electrostatographic copy sheet, and methods of making and using the same
CA1141529A (en) Electroconductive polymers having improved solvent holdout properties
US4168165A (en) Electrophotographic photosensitive material suitable for offset printing and lithography and process for production thereof
US3479215A (en) Coated paper having electroconductive properties and process of making the same
CA1144694A (en) Polymers with improved solvent holdout in electroconductive paper
US3617372A (en) Electroconductive paper
US3642663A (en) Soluble quaternized condensation products of epihalohydrins and polyamines
US3639122A (en) Vinyl-amino resin interlayer for electrophotographic member used in offset printing
US3656949A (en) Method of producing an electrophotographic and electrographic recording member
US3132941A (en) Superior binders for photoconductive layers containing zinc oxide
US3607286A (en) Photographic material comprising an antistatic coating
US3870559A (en) Paper treatment
US3459593A (en) Nonblocking electrostatic sheets
US3900319A (en) Electrostatographic copy paper containing glycidyl quaternary ammonium compounds