US2803171A - Process for producing a water vapor impermeable board - Google Patents
Process for producing a water vapor impermeable board Download PDFInfo
- Publication number
- US2803171A US2803171A US376749A US37674953A US2803171A US 2803171 A US2803171 A US 2803171A US 376749 A US376749 A US 376749A US 37674953 A US37674953 A US 37674953A US 2803171 A US2803171 A US 2803171A
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- US
- United States
- Prior art keywords
- board
- water vapor
- wax
- clay
- emulsion
- 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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Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21J—FIBREBOARD; MANUFACTURE OF ARTICLES FROM CELLULOSIC FIBROUS SUSPENSIONS OR FROM PAPIER-MACHE
- D21J1/00—Fibreboard
- D21J1/08—Impregnated or coated fibreboard
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/017—Mixtures of compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/38—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing crosslinkable groups
- D21H17/39—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing crosslinkable groups forming ether crosslinkages, e.g. alkylol groups
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/60—Waxes
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP 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
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/18—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising waxes
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP 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
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/38—Coatings with pigments characterised by the pigments
- D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP 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
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP 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
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP 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
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21J—FIBREBOARD; MANUFACTURE OF ARTICLES FROM CELLULOSIC FIBROUS SUSPENSIONS OR FROM PAPIER-MACHE
- D21J1/00—Fibreboard
- D21J1/16—Special fibreboard
Definitions
- applicator units which are used for this purpose comprise essentially a screen-covered roll which continuously revolves in a body of bituminous emulsion, maintained in a suitable trough. A film of the emulsified bitumen is picked up by the screen on the roll and is transferred to the surface of a wet fibrous ply as it passes over the applicator roll. Fresh supplies of the emulsion of the requisite consistency are passed into'the trough as the emulsion is taken up by the roll.
- the present invention relates to an improved paper board within which is a film of a composition comprising a major proportion of wax, a minor proportion of solid homopolymer of isobutene, copolymer of isobutene with approximately 2.5% of isoprene or polyethylene and mixtures thereof and clay.
- the water vapor impermeable film is put on the wet plies of the board in the form of an emulsion, utilizing clay as the emulsifying agent, together with a cationic promoter.
- the clay is desirable in that it forms an emulsion which does not migrate substantially in the paper, and permits the paper to drain before drying.
- Petroleum waxes may be used, including paraflin wax, but rnicrocrystalline wax is preferable, since it gives. a film which does not crack or craze easily.
- the clay is selected from the group consisting of ball clay and koalin clay, but kaolin clay has been found preferable.
- the clay stabilized emulsion on drying forms a film which will not flow under heat because of the honey-comb structure of the film.
- Clays such as bentonite are not desirable because of the difliculty of drainage due to highly colloidal gels which are formed and which may permit the sheet to separate.
- the isobutene polymer should be a substantially solid material which is somewhat elastomeric in nature, hav ing a molecular weight in the range 30,000 to 150,000.
- the polyethylene should be a substantially solid resinous material, or in other words, having a molecular weight in the range 7,000 to 25,000.
- the invention is primarily concerned with either of these two materials or with mixtures thereof, or with mixtures of either one and small amounts of other resins.
- substantially pure isobutene polymer is used.
- the most preferable material is GRI or butyl rubber, which is a copolymer of substantially pure isobutene copolymerized with approximately 2.5 of isoprene.
- Another suitable commercial product is known as Vistanex, which is similar to the butyl rubber but does not contain isoprene.
- the amount of polymer should be in the range 5 to 45% of the total polymer wax composition, and is preferably about 25%. Mixtures of the two polymers found particularly suitable include 5 parts polyethylene, 20 parts isobutene polymer and parts wax. In any case, a desirable composition of polymer and wax should have a viscosity of about 100,000 centipoises at to 220 F.
- the cationic promoter may be any cationic surface active agent. Of these, it has been found preferable to use an amine known commercially as Armeen H. T. D., which is approximately 25% hexadecyl amine, 70% octadecyl amine and 5% octadecenyl amine.
- Armeen H. T. D. which is approximately 25% hexadecyl amine, 70% octadecyl amine and 5% octadecenyl amine.
- the cationic surface active agents are illustrated by the following:
- Dodecylamine i alkyl alkyl I Basic pyridinium compounds and their salts.
- Methyl sulfate of dirnethyloctadecyl sulfonium Betaine compounds of quaternary ammonium Methyl sulfate of dirnethyloctadecyl sulfonium Betaine compounds of quaternary ammonium.
- Menthol diurethane hydrochloride Polyethylene diamines and their quaternary ammonium derivatives. 0. Polypropanol polyethanolamines.
- the polyisobutene was placed in a slightly warm Banbury mixer. The batch was mixed until the temperature rose to 250-300 F. and then about A of the total wax was added. This was repeated 3 times, the wax being added only when the temperature was between 250 and 300 F.
- the master batch was mixed with about 45 parts wax in a Baker-Perkins dispersion mixer heated to about 100 to 120 F. When a homogeneous blend was produced, 45 parts more of wax were added. As soon as the blend again became homogeneous, the remainder of the wax was added. After waiting several minutes and then raising the temperature of the blend to 195200 F., the alkyl amine was added. At this point the mixer was stopped and the entire clay slip quickly added. The mixer was immediately started and the temperature maintained at 180 F. after which the blend inverted. After a few minutes the mixture assumed a homogeneous appearance and part of the water at 210 F. was added gradually for several minutes. Thereafter, the rest of the water at room temperature was added and the lignin sulphonate solution added. The emulsion was passed through a 30 mesh screen and stored in polyethylene lined drums.
- the emulsion of this example was diluted with equal parts of water and delivered to an application apparatus on a paper machine of the type adapted to apply bituminous emulsion to wet plies.
- the usual device for application is a wire covered cylinder immersed in a bath of the emulsion maintained at a constant level.
- the finished board made on the machine was tested after passing through the drying rolls and stacked in the usual manner. Examination of the sheet showed that the film had not migrated, and the plies adhered satisfactorily.
- a process for producing a water vapor impermeable paper board comprising applying to a wet inner ply of the board on a cylinder machine an emulsion comprising water, a major proportion of petroleum wax, a minor proportion of a solid polymer selected from the group consisting of homopolymers of isobutene, copolymers of isobutene with approximately 2.5% of isoprene and polyethylene and mixtures thereof, a clay selected from the group consisting of kaolin and ball clay, and a cationic surface active agent, and wherein the ratio of the combined wax and polymer is 3 to 10 parts per part of clay, applying at least one ply over the emulsion, draining the water and drying the board in the usual manner.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Paper (AREA)
Description
United States Patent PROCESS FOR PRODUCING A WATER- VAPOR IMPERMEABLE BOARD Richard H. Cuhberley, Morris Township, and M. Benjamin Dell, Morristown, N. J., assignors to The Patent and Licensing Corporation, New York, N. Y., a corporation of Massachusetts Application August 26, 1953, Serial No. 376,749
1 Claim. (Cl. 92-41) No Drawing.
applicator units which are used for this purpose comprise essentially a screen-covered roll which continuously revolves in a body of bituminous emulsion, maintained in a suitable trough. A film of the emulsified bitumen is picked up by the screen on the roll and is transferred to the surface of a wet fibrous ply as it passes over the applicator roll. Fresh supplies of the emulsion of the requisite consistency are passed into'the trough as the emulsion is taken up by the roll.
Process and apparatus for coating the wet plies in this manner are described, for example, in U. S. Patents Nos. 1,686,818; 1,722,432; 1,724,137 and 1,732,361 and more recent improvements are found in U. S. Patents Nos. 2,622,313 and 2,622,491. This has provided a material which is resistant to the passage of water vapor and wherein the vapor-proofing medium is inexpensively applied and substantially protected from removal when the board is folded, as might be the case with surface coated board. The bituminous material is of such a nature that the coating between the plies does not initially prohibit the water from draining off the paper, and yet after passing through drier rolls, a continuous film is formed which is resistant to the passage of water vapor.
While this process and the product thereof has been found highly successful for many years, nevertheless, in certain applications such as containers for food, it is more desirable to have a material not possessing the black 'color of the bitumen and having a somewhat greater water vapor impermeability. Furthermore, in many applications it is desirable to have a grease barrier such as in the packaging of doughnuts, potato chips, etc. Such'a product should contain all of the other desirable features of the bituminous coating process, including the fact that the coating does not come in contact with the contents of the containers which may be made from the board, and also does not interfere with the printing, folding or gluing of the board.
It is, therefore, a principal object of the present inven tion to provide an improved paper board which is water vapor impermeable.
It is a further object of the present invention to provide an improved paper board which is resistant to the passage of grease. 4 I
It is a further object of the present inventionto provide a paper board having a material applied between the plies thereof which is light in color, folds without cracking, and is water vapor impermeable.
2,803,171 Patented Aug. 20, 1957 It is a further object of the present invention to provide an improved process for making paper board, including the application to the wet plies thereof, of a material which forms a film in the dry board which is of a light color, resistant to the passage of grease, folds without cracking, and is impermeable to water vapor.
These and other objects are attained by the present invention which relates to an improved paper board within which is a film of a composition comprising a major proportion of wax, a minor proportion of solid homopolymer of isobutene, copolymer of isobutene with approximately 2.5% of isoprene or polyethylene and mixtures thereof and clay. v
The water vapor impermeable film is put on the wet plies of the board in the form of an emulsion, utilizing clay as the emulsifying agent, together with a cationic promoter. The clay is desirable in that it forms an emulsion which does not migrate substantially in the paper, and permits the paper to drain before drying.
In order to obtain the desirable ratio of isobutene polymer or polyethylene and wax to clay, it has been found necessary to utilize a cationic promoter. For example, a ratio of 2 /2 parts of isobutene polymer and wax tofl part of kaolin clay will form :an unstable emulsion without a promoter. However, in order to obtain ratios of 3 to 10 parts 'of isobutene polymer wax per part of kaolin clay in a stable emulsion, it is necessary to use a promoter. It has been found that a cationic promoter such as an alkyl amine is efiective.
Petroleum waxes may be used, including paraflin wax, but rnicrocrystalline wax is preferable, since it gives. a film which does not crack or craze easily.
The clay is selected from the group consisting of ball clay and koalin clay, but kaolin clay has been found preferable. The clay stabilized emulsion on drying forms a film which will not flow under heat because of the honey-comb structure of the film. Clays such as bentonite are not desirable because of the difliculty of drainage due to highly colloidal gels which are formed and which may permit the sheet to separate.
The isobutene polymer should be a substantially solid material which is somewhat elastomeric in nature, hav ing a molecular weight in the range 30,000 to 150,000. The polyethylene should be a substantially solid resinous material, or in other words, having a molecular weight in the range 7,000 to 25,000. The invention is primarily concerned with either of these two materials or with mixtures thereof, or with mixtures of either one and small amounts of other resins. Preferably, however, substantially pure isobutene polymer is used. The most preferable material is GRI or butyl rubber, which is a copolymer of substantially pure isobutene copolymerized with approximately 2.5 of isoprene. Another suitable commercial product is known as Vistanex, which is similar to the butyl rubber but does not contain isoprene.
The amount of polymer should be in the range 5 to 45% of the total polymer wax composition, and is preferably about 25%. Mixtures of the two polymers found particularly suitable include 5 parts polyethylene, 20 parts isobutene polymer and parts wax. In any case, a desirable composition of polymer and wax should have a viscosity of about 100,000 centipoises at to 220 F.
The cationic promoter may be any cationic surface active agent. Of these, it has been found preferable to use an amine known commercially as Armeen H. T. D., which is approximately 25% hexadecyl amine, 70% octadecyl amine and 5% octadecenyl amine. The cationic surface active agents are illustrated by the following:
A. Aliphatic amines and their derivatives.
Dodecylamine i alkyl alkyl I. Basic pyridinium compounds and their salts.
Octadecyl methylene pyridinium acetate J. Basie sulfonium, phosphonium and antimonium compounds.
Methyl sulfate of dirnethyloctadecyl sulfonium Betaine compounds of quaternary ammonium.
Hydrochloride of dimethyloctadecyhnethyl aminoacetate Dimethylphenylbenzyl ammonium chloride. Urethanes or basic salts of ethylene diamine.
Menthol diurethane hydrochloride Polyethylene diamines and their quaternary ammonium derivatives. 0. Polypropanol polyethanolamines.
EXAMPLE All equipment should be clean to prevent discoloration of the emulsion. The water used should be substantially free of sulfur compounds.
Preparation of master batch Parts Polyisobutene (GRI-17) 96.5 Microcrystalline wax M. P.180 F., 30 pen. at
The polyisobutene was placed in a slightly warm Banbury mixer. The batch was mixed until the temperature rose to 250-300 F. and then about A of the total wax was added. This was repeated 3 times, the wax being added only when the temperature was between 250 and 300 F.
Preparation of emulsion Parts Master batch 150 r Microcrystalline wax 236 Alkyl amine (Armeen H. T. D.) 0.2
Clay slip at 210 F.:
77.1 parts of kaolin clay (Crossman clay) 154.2 parts water Lignin sulphonate: 0.25 part of lignin sulphonate (Marasperse N) was dissolved in 1 part of Water heated between 140 and 150 F.
Water 223 The master batch was mixed with about 45 parts wax in a Baker-Perkins dispersion mixer heated to about 100 to 120 F. When a homogeneous blend was produced, 45 parts more of wax were added. As soon as the blend again became homogeneous, the remainder of the wax was added. After waiting several minutes and then raising the temperature of the blend to 195200 F., the alkyl amine was added. At this point the mixer was stopped and the entire clay slip quickly added. The mixer was immediately started and the temperature maintained at 180 F. after which the blend inverted. After a few minutes the mixture assumed a homogeneous appearance and part of the water at 210 F. was added gradually for several minutes. Thereafter, the rest of the water at room temperature was added and the lignin sulphonate solution added. The emulsion was passed through a 30 mesh screen and stored in polyethylene lined drums.
The emulsion of this example was diluted with equal parts of water and delivered to an application apparatus on a paper machine of the type adapted to apply bituminous emulsion to wet plies. The usual device for application is a wire covered cylinder immersed in a bath of the emulsion maintained at a constant level. The finished board made on the machine was tested after passing through the drying rolls and stacked in the usual manner. Examination of the sheet showed that the film had not migrated, and the plies adhered satisfactorily.
Water vapor permeability tests were made by covering weighed dishes of anhydrous calcium chloride with samples of board, placing the dishes in a constant humidity apparatus such as the General Foods cabinet, and then weighing the dishes again at stated time intervals. The
tests are ASTM tests D988-51T. The average water vapor transmission of the sheet was very low, averaging about 0.4 gram of water per 100 square inches of board per 24 hours at 100 F. with relative humidity for 10 lbs. blend per 1000 square feet of board. This com pares with a moisture vapor transmission of 2.5 grams for a coverage of about'20 lbs. per 1000 square feet of bitumen.
We claim:
A process for producing a water vapor impermeable paper board comprising applying to a wet inner ply of the board on a cylinder machine an emulsion comprising water, a major proportion of petroleum wax, a minor proportion of a solid polymer selected from the group consisting of homopolymers of isobutene, copolymers of isobutene with approximately 2.5% of isoprene and polyethylene and mixtures thereof, a clay selected from the group consisting of kaolin and ball clay, and a cationic surface active agent, and wherein the ratio of the combined wax and polymer is 3 to 10 parts per part of clay, applying at least one ply over the emulsion, draining the water and drying the board in the usual manner.
References Cited in the file of this patent UNITED STATES PATENTS Re. 15,461 Perry Sept. 26, 1922 58,944 Hurlbut Oct. 16, 1866 852,918 White May 7, 1907 1,616,902 Kirschbraun Feb. 8, 1927 1,621,888 Kirschbraun Mar. 22, 1927 2,343,090 Smith Feb. 29, 1944 2,343,095 Smith Feb. 29, 1944 2,416,447 Laughlin et a1. Feb. 25, 1947 2,487,899 Sherman Nov. 15, 1949 2,492,702 Neubert et al Dec. 27, 1949 2,493,604 Walters Jan. 3, 1950 2,510,661 Safiord June 6, 1950 2,563,897 Wilson et al. Aug. 14, 1951 2,582,037 Hyde Jan. 8, 1952 2,610,939 Fisher Sept. 16, 1952 2,626,213 Novak Jan. 20, 1953 2,649,386 Snowman Aug. 18, 1953 2,658,828 Pattilloch Nov. 10, 1953 FOREIGN PATENTS 178,155 Great Britain Apr. 12, 1922 664,239 Great Britain Jan. 2, 1952
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US376749A US2803171A (en) | 1953-08-26 | 1953-08-26 | Process for producing a water vapor impermeable board |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US376750A US2859190A (en) | 1953-08-26 | 1953-08-26 | Wax-resin emulsion for water vapor proofing paper and method of producing same |
US376749A US2803171A (en) | 1953-08-26 | 1953-08-26 | Process for producing a water vapor impermeable board |
Publications (1)
Publication Number | Publication Date |
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US2803171A true US2803171A (en) | 1957-08-20 |
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US376749A Expired - Lifetime US2803171A (en) | 1953-08-26 | 1953-08-26 | Process for producing a water vapor impermeable board |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2973285A (en) * | 1958-12-31 | 1961-02-28 | Dow Chemical Co | Preparation of coated articles using gellable aqueous cationic polymer coating compositions and printing inks |
US3294728A (en) * | 1962-01-27 | 1966-12-27 | Hoechst Ag | Process for preparing dispersions of olefin polymers containing positively charged particles with tertiary or quaternary ammonium ethoxylated fatty amines |
US3294618A (en) * | 1965-04-22 | 1966-12-27 | John A Manning Paper Co Inc | Paper product |
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-
1953
- 1953-08-26 US US376749A patent/US2803171A/en not_active Expired - Lifetime
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US2649386A (en) * | 1948-02-21 | 1953-08-18 | North American Paper Process C | Coated paper and method for making same |
US2658828A (en) * | 1948-09-15 | 1953-11-10 | Chemloch Corp | Process of combining synthetic resins and other materials with cellulose |
GB664239A (en) * | 1948-11-25 | 1952-01-02 | Ernst Georg Josef Froehlich | Improvements in and relating to the treatment of paper with liquids during its manufacture |
US2626213A (en) * | 1948-12-21 | 1953-01-20 | Raybestos Manhattan Inc | Asbestos dispersions and method of forming same |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2973285A (en) * | 1958-12-31 | 1961-02-28 | Dow Chemical Co | Preparation of coated articles using gellable aqueous cationic polymer coating compositions and printing inks |
US3294728A (en) * | 1962-01-27 | 1966-12-27 | Hoechst Ag | Process for preparing dispersions of olefin polymers containing positively charged particles with tertiary or quaternary ammonium ethoxylated fatty amines |
US3294618A (en) * | 1965-04-22 | 1966-12-27 | John A Manning Paper Co Inc | Paper product |
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