US3310460A - Sizing composition of starch and a reaction product of an isocyanate with an alkylene imine and process of sizing paper therewith - Google Patents

Sizing composition of starch and a reaction product of an isocyanate with an alkylene imine and process of sizing paper therewith Download PDF

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US3310460A
US3310460A US341156A US34115663A US3310460A US 3310460 A US3310460 A US 3310460A US 341156 A US341156 A US 341156A US 34115663 A US34115663 A US 34115663A US 3310460 A US3310460 A US 3310460A
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imine
sizing
starch
reaction product
isocyanate
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US341156A
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Goldstein Albert
John W Brook
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Chemirad Corp
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Chemirad Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D203/00—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom
    • C07D203/04—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
    • C07D203/06—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D203/08—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring nitrogen atom
    • 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
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • 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
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • 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
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/57—Polyureas; Polyurethanes
    • 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
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents

Definitions

  • the present invention relates to a new and valuable process of sizing and improving the properties of paper and the like material and to compositions used in such sizing operations.
  • Sized paper has a better surface for accepting writing or printing inks.
  • Sizes containing casein or glue as well as rosin sizing agents are used chiefly for sizing paper, paper board, and pulp products.
  • Other sizing agents for paper are, for instance, the alkyl ketene dimers of the Aquapel type as sold by Hercules Powder Co. and certain aliphatic fatty acids.
  • the rosin type sizing agents and the fatty acids require fixation by means of alum and usually operation at a low pH-value. at a low pH, however, is disadvantageously affected inasmuch as its aging properties are impaired.
  • acid reaction of the paper pulp causes corrosion of the paper making machinery. Paper made under acidic conditions is unsuitable for many purposes because of its unwanted stiffness. Therefore, many attempts have been made to provide sizing agents which work under neutral or alkaline conditions. However, heretofore, such attempts have been rather unsuccessful.
  • alkyl ketene dimer sizing agents mentioned above have been used for sizing under neutral or alkaline conditions.
  • Such alkyl ketene dimers have the disadvantage that they require a prolonged curing time in order to develop optimum properties. They are also temperature sensitive when used in a paper making system. For this reason, they cannot be used, for instance, at a temperature of about 60 C. or higher.
  • Another object of the present invention is to provide a simple and effective process, of sizing paper by the addition of such sizing compositions to the paper pulp before or during paper forming.
  • the sizing compositions according to the present invention are characterized by containing, as active sizing ingredients, the reaction product of a long chain aliphatic isocyanate and an alkylene imine.
  • reaction products are the reaction products of aliphatic isocyanates and especially of octadecyl isocyanate and ethylene imine.
  • Other aliphatic isocyanates which contain between 10 carbon atoms and 20 carbon atoms in their aliphatic chain may also be used, likewise other alkylene imines which are substituted at their carbon atoms, such as the Z-methyl ethylene imine, 2-ethyl Paper sized ethylene imine, 2,2-dimethyl ethylene imine, 2,3-butylene imine, and the like.
  • Reaction between such long chain aliphatic isocyanates and alkylene imine may be carried out in any of the known procedures whereby reaction may occur either in an aqueous medium or in an organic system.
  • reaction emulsion may be added in combination with a retention aid to the paper pulp slurry.
  • a retention aid is, for instance, polyethylene imine.
  • polyalkylene imines may, of course, also be used as well as other retention aids such as the polyamideepichlorohydrin resins as they are sold for instance, under the trademark Kymene 557 by Hercules Powder Co., the retention aid sold under the trademark Reten 763 by Hercules Powder Co., the cationic starch derivative sold under the trademark Cato-8 by National Starch and Chemical Corp, and others.
  • reaction products of alkylene imines with long chain aliphatic isocyanates more particularly the reaction products of ethylene imine and octadecyl isocyanate have been found to beneficially affect surface sizing of paper and paper board as normally practiced by tub or calender-stack sizing techniques.
  • emulsions of the reaction products according to the present invention may be used. It is, however, also possible to use an aqueous dispersion of the reaction products which preferably is prepared from the solid reaction product by dispersing it, together with wax and starch or other surface sizing agents, in water.
  • Solid reaction products of alkylene imines and long chain aliphatic isocyanates as they are used for making dispersions with wax and/or starch are obtained by carrying out the reaction in an organic solvent, for instance, in hexane and other wherein the reaction product is insoluble and precipitates.
  • reaction mixture Upon completing the addition, the reaction mixture is adjusted to a pH of 9.0 by the addition of ammonia solution and is agitated for two hours at about 25 C. The product mixture is then passed through a homogenizer in order to produce a uniform product.
  • Example 2 A solution of 200 parts of octadecyl isocyanate in 300 parts of hexane is added to a stirred solution of 30 parts of ethylene imine in 400 parts of hexane at a temperature of 25 C. The reaction temperature is maintained at 2530 C. during the addition and for one hour after completing the addition. The reaction product is then isolated by filtration and dried. Its melting point is 7073 C.
  • Example 3 Sufiicient amounts of the product of Example 1 were added to an unbleached hardwood kraft pulp of 26 S-R freeness, at a consistency of 0.25%, to give a 0.5% additional level of the active product (octadecyl ethylene urea). Handsheets were formed at a basis weight of 51 lb. (24 36500). The sheets were pressed, dried for 3 minutes at 95 C. and conditioned at 25 C. and 50% RH.
  • sheets were produced containing 1.5% of the compound of Example 1 and 0.5% and 1.5 of the compound of Example 1 plus 0.1% of polyethylene mine.
  • the conditioned sheets were tested for sizing, i.e., resistance to water penetration, by the Cobb test (TAPPI T441m60) with water and by the flotation test (TAPPI RC-72) with 2% sodium hydroxide solution.
  • Example 4 One part of the product of Example 2 and 4.1 parts of water were added to 37.4 parts of a starch size solution consisting of 200 parts of tapioca starch, 5 parts of wax, 0.5 part of soap, 0.25 part of sodium silicate, 1 part of sodium sulfite, and 3800 parts of water.
  • This aqueous dispersion contains about 2.3 percent of the reaction product of octadecyl isocyanate and ethylene imine, about 4.4 percent of a tapioca starch, and about 0.1 percent of a wax.
  • the resulting dispersion was applied to paper board through the water box on the calendar stack of a paper machine.
  • the resulting board surface was tested, in comparison to a standard board treated with the unmodified size solution, for water absorbency and wet scuff resistance.
  • reaction product of octadecyl isocyanate with ethylene imine as prepared and used in the preceding examples, there may be employed, as the one reaction component, equimolecular amounts of other long chain aliphatic isocyanates such as decyl isocyanate, hexadecyl isocyanate, and others as well as other alkylene imines such as 1,2-pr-opylene imine, 1,2-butylene imine, 2,3- butylene imine, or mixtures of ethylene imine with propylene imine and other alkylene imines, while other Wise the procedure is the same as described in said examples.
  • other long chain aliphatic isocyanates such as decyl isocyanate, hexadecyl isocyanate, and others as well as other alkylene imines such as 1,2-pr-opylene imine, 1,2-butylene imine, 2,3- butylene imine, or mixtures of ethylene imine with prop
  • a composition for sizing cellulosic sheet material comprising an aqueous dispersion having (a) from approximately 2 to 20 percent of the reaction product of a long chain aliphatic isocyanate with between 10 and 20 carbon atoms in the aliphatic chain and an alkylene imine selected from the class consisting of ethylene imine, 1,2-propylene imine, and 1,2-butylene imine, and
  • composition of claim 1 wherein the aliphatic isocyanate is octadecyl isocyanate and the alkylene imine is ethylene imine.
  • composition of claim 2 containing, additionally, about 0.1 percent of a wax.
  • a process for sizing cellulosic fibrous material comprising adding to an aqueous cellulosic fiber dispersion an aqueous dispersion having about 2 to 20 percent of the reaction product of an aliphatic isocyanate with from 10 to 20 carbon atoms in its aliphatic chain and an alkylene imine selected from the class consisting of ethylene imine, 1,2-propylene imine, and 1,2-butylene imine and about 4 percent of a starch; and forming cellulosic sheet material from the thus treated dispersion.

Description

United States Patent SIZING COMPOSITION OF STARCH AND A RE- ACTION PRDDUCT OF AN ISOCYANATE WITH AN ALKYLENE IMHNE AND PROCESS OF SIZ- IN G PAPER THEREWITH Albert Goldstein, New Shrewsbury, and John W. Brook,
East Brunswick, N.J., assignors to Chemirad Corporation, East Brunswick, N.J., a corporation of Delaware No Drawing. Filed Dec. 31, 1963, Ser. No. 341,156
6 Claims. (Cl. 162-164) The present invention relates to a new and valuable process of sizing and improving the properties of paper and the like material and to compositions used in such sizing operations.
It is known toimprove the surface properties of paper by a treatment of the paper pulp and/or the finished paper sheet with a sizing agent.
Sized paper has a better surface for accepting writing or printing inks. Sizes containing casein or glue as well as rosin sizing agents are used chiefly for sizing paper, paper board, and pulp products. Other sizing agents for paper are, for instance, the alkyl ketene dimers of the Aquapel type as sold by Hercules Powder Co. and certain aliphatic fatty acids. The rosin type sizing agents and the fatty acids require fixation by means of alum and usually operation at a low pH-value. at a low pH, however, is disadvantageously affected inasmuch as its aging properties are impaired. Furthermore, acid reaction of the paper pulp causes corrosion of the paper making machinery. Paper made under acidic conditions is unsuitable for many purposes because of its unwanted stiffness. Therefore, many attempts have been made to provide sizing agents which work under neutral or alkaline conditions. However, heretofore, such attempts have been rather unsuccessful.
The known alkyl ketene dimer sizing agents mentioned above have been used for sizing under neutral or alkaline conditions. Such alkyl ketene dimers, however, have the disadvantage that they require a prolonged curing time in order to develop optimum properties. They are also temperature sensitive when used in a paper making system. For this reason, they cannot be used, for instance, at a temperature of about 60 C. or higher.
It is one object of the present invention to provide new and valuable sizing compositions which can be used under neutral and alkaline conditions and which are sub stantially free of the disadvantages of the known sizing agents.
Another object of the present invention is to provide a simple and effective process, of sizing paper by the addition of such sizing compositions to the paper pulp before or during paper forming.
Other objects of the present'invention and advantageous features thereof will become apparent as the description proceeds.
In principle the sizing compositions according to the present invention are characterized by containing, as active sizing ingredients, the reaction product of a long chain aliphatic isocyanate and an alkylene imine. The,
preferred reaction products are the reaction products of aliphatic isocyanates and especially of octadecyl isocyanate and ethylene imine. Other aliphatic isocyanates which contain between 10 carbon atoms and 20 carbon atoms in their aliphatic chain may also be used, likewise other alkylene imines which are substituted at their carbon atoms, such as the Z-methyl ethylene imine, 2-ethyl Paper sized ethylene imine, 2,2-dimethyl ethylene imine, 2,3-butylene imine, and the like.
Reaction between such long chain aliphatic isocyanates and alkylene imine may be carried out in any of the known procedures whereby reaction may occur either in an aqueous medium or in an organic system.
It has been found to be of advantage to prepare such reaction products in an aqueous system containing an emulsifying agent. Especially advantageous emulsifiers for this purpose are, for instance, the sorbitan monooleate polyalkylene derivative sold under the trademark Tween 80 by Atlas Powder Company of Wilmington, Del, the emulsifier sold under the trademark Gafac RE-6l0 by Antara Chemicals of New York, N.Y.; and others. By operating in this manner it is possible to obtain the desired reaction product in the form of an aqueous emulsion which can directly be applied to a paper pulp slurry. It is also possible to apply such an emulsion to the finished paper sheet. If too concentrated, the emulsion of the reaction product may be applied after dilution with water.
According to another embodiment of this invention the reaction emulsion may be added in combination with a retention aid to the paper pulp slurry. An especially suitable retention aid is, for instance, polyethylene imine.
Other polyalkylene imines may, of course, also be used as well as other retention aids such as the polyamideepichlorohydrin resins as they are sold for instance, under the trademark Kymene 557 by Hercules Powder Co., the retention aid sold under the trademark Reten 763 by Hercules Powder Co., the cationic starch derivative sold under the trademark Cato-8 by National Starch and Chemical Corp, and others.
According to another embodiment of the present invention the reaction products of alkylene imines with long chain aliphatic isocyanates, more particularly the reaction products of ethylene imine and octadecyl isocyanate have been found to beneficially affect surface sizing of paper and paper board as normally practiced by tub or calender-stack sizing techniques. For this purpose emulsions of the reaction products according to the present invention may be used. It is, however, also possible to use an aqueous dispersion of the reaction products which preferably is prepared from the solid reaction product by dispersing it, together with wax and starch or other surface sizing agents, in water. When using such compov sitions containing dispersions of the reaction product of alkylene imines with long chain aliphatic isocyanates together with starch and/or wax, the sizing affect of the known starch and/or wax dispersions is greatly enhanced.
Solid reaction products of alkylene imines and long chain aliphatic isocyanates as they are used for making dispersions with wax and/or starch, are obtained by carrying out the reaction in an organic solvent, for instance, in hexane and other wherein the reaction product is insoluble and precipitates.
The following examples serve to illustrate the present invention, without, however, limiting the same thereto.
' Example 1 range of 25 Cjto 35 C.
Upon completing the addition, the reaction mixture is adjusted to a pH of 9.0 by the addition of ammonia solution and is agitated for two hours at about 25 C. The product mixture is then passed through a homogenizer in order to produce a uniform product.
Example 2 A solution of 200 parts of octadecyl isocyanate in 300 parts of hexane is added to a stirred solution of 30 parts of ethylene imine in 400 parts of hexane at a temperature of 25 C. The reaction temperature is maintained at 2530 C. during the addition and for one hour after completing the addition. The reaction product is then isolated by filtration and dried. Its melting point is 7073 C.
Example 3 Sufiicient amounts of the product of Example 1 were added to an unbleached hardwood kraft pulp of 26 S-R freeness, at a consistency of 0.25%, to give a 0.5% additional level of the active product (octadecyl ethylene urea). Handsheets were formed at a basis weight of 51 lb. (24 36500). The sheets were pressed, dried for 3 minutes at 95 C. and conditioned at 25 C. and 50% RH.
In a similar manner, sheets were produced containing 1.5% of the compound of Example 1 and 0.5% and 1.5 of the compound of Example 1 plus 0.1% of polyethylene mine.
The conditioned sheets were tested for sizing, i.e., resistance to water penetration, by the Cobb test (TAPPI T441m60) with water and by the flotation test (TAPPI RC-72) with 2% sodium hydroxide solution.
The results obtained were as shown below in Table I:
Cobb Sizing Flotation (sec.
Example 4 One part of the product of Example 2 and 4.1 parts of water were added to 37.4 parts of a starch size solution consisting of 200 parts of tapioca starch, 5 parts of wax, 0.5 part of soap, 0.25 part of sodium silicate, 1 part of sodium sulfite, and 3800 parts of water. This aqueous dispersion contains about 2.3 percent of the reaction product of octadecyl isocyanate and ethylene imine, about 4.4 percent of a tapioca starch, and about 0.1 percent of a wax.
The resulting dispersion was applied to paper board through the water box on the calendar stack of a paper machine.
The resulting board surface was tested, in comparison to a standard board treated with the unmodified size solution, for water absorbency and wet scuff resistance.
In place of the reaction product of octadecyl isocyanate with ethylene imine as prepared and used in the preceding examples, there may be employed, as the one reaction component, equimolecular amounts of other long chain aliphatic isocyanates such as decyl isocyanate, hexadecyl isocyanate, and others as well as other alkylene imines such as 1,2-pr-opylene imine, 1,2-butylene imine, 2,3- butylene imine, or mixtures of ethylene imine with propylene imine and other alkylene imines, while other Wise the procedure is the same as described in said examples.
We claim: I
1. A composition for sizing cellulosic sheet material comprising an aqueous dispersion having (a) from approximately 2 to 20 percent of the reaction product of a long chain aliphatic isocyanate with between 10 and 20 carbon atoms in the aliphatic chain and an alkylene imine selected from the class consisting of ethylene imine, 1,2-propylene imine, and 1,2-butylene imine, and
(b) about 4 percent of a starch.
2. The composition of claim 1 wherein the aliphatic isocyanate is octadecyl isocyanate and the alkylene imine is ethylene imine.
3. The composition of claim 2 containing, additionally, about 0.1 percent of a wax.
4. A process for sizing cellulosic fibrous material comprising adding to an aqueous cellulosic fiber dispersion an aqueous dispersion having about 2 to 20 percent of the reaction product of an aliphatic isocyanate with from 10 to 20 carbon atoms in its aliphatic chain and an alkylene imine selected from the class consisting of ethylene imine, 1,2-propylene imine, and 1,2-butylene imine and about 4 percent of a starch; and forming cellulosic sheet material from the thus treated dispersion.
5. The process of claim 4 wherein the aliphatic isocyanate is octadecyl isocyanate and the alkylene imine is ethylene imine.
6. The process of claim 5 wherein said dispersion contains about 2.3 percent of the reaction product of octadecyl isocyanate and ethylene imine, about 4.4 percent of a starch, and about 0.1 percent of a wax.
References Cited by the Examiner UNITED STATES PATENTS 2,341,413 2/1944 Pense et a1. 2602 3,084,092 4/ 1963 Arlt 162166 FOREIGN PATENTS 681,520 9/ 1939 Germany. 466,344 5 1937 Great Britain. 467,655 12/ 1951 Italy.
DONALL H. SYLVESTER, Primary Examiner.
S. LEON BASHORE, Examiner.

Claims (2)

1. A COMPOSITION FOR SIZING CELLULOSIC SHEET MATERIAL COMPRISING AN AQUEOUS DISPERSION HAVING (A) FROM APPROXIMATELY 2 TO 20 PERCENT OF THE REACTION PRODUCT OF A LONG CHAIN ALIPHATIC ISOCYANATE WITH BETWEEN 10 AND 20 CARBON ATOMS IN THE ALIPHATIC CHAIN AND AN ALKYLENE IMINE SELECTED FROM THE CLASS CONSISTING OF ETHYLENE IMINE, 1,2-PROPYLENE IMINE, AND 1,2-BUTYLENE IMINE, AND (B) ABOUT 4 PERCENT OF A STARCH.
4. A PROCESS FOR SIZING CELLULOSIC FIBROUS MATERIAL COMPRISING ADDING TO AN AQUEOUS CELLULOSIC FIBER DISPERSION AN AQUEOUS DISPERSION HAVING ABOUT 2 TO 20 PERCENT OF THE REACTION PRODUCT OF AN ALIPHATIC ISOCYANATE WITH FROM 10 TO 20 CARBON ATOMS IN ITS ALIPHATIC CHAIN AND AN ALKYLENE IMINE SELECTED FROM THE CLASS CONSISTING OF ETHYLENE IMINE, 1,2-PROPYLENE IMINE, AND 1,2-BUTYLENE IMINE AND ABOUT 4 PERCENT OF A STARCH; AND FORMING CELLULOSIC SHEET MATERIAL FROM THE THUS TREATED DISPERSION.
US341156A 1963-12-31 1963-12-31 Sizing composition of starch and a reaction product of an isocyanate with an alkylene imine and process of sizing paper therewith Expired - Lifetime US3310460A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3627631A (en) * 1969-12-08 1971-12-14 Sun Chemical Corp A method of waterproofing paper using an n{40 -alkyl, n{hd 1{l {40 n{hd 1{l {40 -alkylene-n,n{hd 1{l -bis-urea
US3642571A (en) * 1969-12-08 1972-02-15 Sun Chemical Corp A method of sizing cellulosic fibers using an n,n,-(x-alkyl)-n-carbamate{13 (n{11 {40 ,n{11 {40 -alkylen)urea

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB466344A (en) * 1935-08-22 1937-05-24 Ig Farbenindustrie Ag Improvements in the manufacture and production of nitrogenous products
DE681520C (en) * 1935-08-16 1939-09-25 I G Farbenindustrie Akt Ges Process for the production of nitrogen-containing products from alkyleneimines
US2341413A (en) * 1939-09-27 1944-02-08 Pense Walter Process of preparing coatings and the materials thus obtained
US3084092A (en) * 1959-06-16 1963-04-02 American Cyanamid Co Sized paper manufacture

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE681520C (en) * 1935-08-16 1939-09-25 I G Farbenindustrie Akt Ges Process for the production of nitrogen-containing products from alkyleneimines
GB466344A (en) * 1935-08-22 1937-05-24 Ig Farbenindustrie Ag Improvements in the manufacture and production of nitrogenous products
US2341413A (en) * 1939-09-27 1944-02-08 Pense Walter Process of preparing coatings and the materials thus obtained
US3084092A (en) * 1959-06-16 1963-04-02 American Cyanamid Co Sized paper manufacture

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3627631A (en) * 1969-12-08 1971-12-14 Sun Chemical Corp A method of waterproofing paper using an n{40 -alkyl, n{hd 1{l {40 n{hd 1{l {40 -alkylene-n,n{hd 1{l -bis-urea
US3642571A (en) * 1969-12-08 1972-02-15 Sun Chemical Corp A method of sizing cellulosic fibers using an n,n,-(x-alkyl)-n-carbamate{13 (n{11 {40 ,n{11 {40 -alkylen)urea

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