Classifications

• • 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
  • D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
• • 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
  • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
  • D21H13/36—Inorganic fibres or flakes
  • D21H13/38—Inorganic fibres or flakes siliceous
  • D21H13/42—Asbestos
• • 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
• • 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
  • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
• • 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
  • D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
  • D21H23/76—Processes or apparatus for adding material to the pulp or to the paper characterised by choice of auxiliary compounds which are added separately from at least one other compound, e.g. to improve the incorporation of the latter or to obtain an enhanced combined effect
  • D21H23/765—Addition of all compounds to the pulp

Definitions

• the present invention relates to a method of making the same.
• present invention is concerned with a fibrous body which consists of a mixture of fibers and of thermoplastic synthetic non-fibrous material.
• a sheet-like body consisting essentially of an intimate mixture of a fibrous material and of a relatively large proportion of a plastic non-fibrous material.
• the present invention contemplates in a method of producing a shaped body consisting essentially of an intimate mixture of a fibrous material and a thermoplastic material interposed between and adhering to the fibers of the fibrous material, the steps of introducing into a fibrous pulp consisting essentially of a suspension of fibers in water finely subdivided thermoplastic material, a water-soluble nitrogenous base of high molecular weight and a water-soluble salt of a carboxylic acid of high molecular weight, so as to form on the fibers a water insoluble reaction product of the nitrogenous base and the salt of a carboxylic acid, the thus formed reaction product facilitating adherence of the finely subdivided thermoplastic material to the fibers, removing at least a portion of the Water of the thus treated pulp so as to obtain a fibrous mass consisting essentially of the fibers having the thermoplastic material adhered thereto and adapted to be shaped into a shape retaining body.
• the present invention is also concerned with a fibrous sheet as an article of manufacture, which fibrous sheet comprises, in combination, a layer of haphazardly arranged fibrous material, a plastic material substantially evenly distributed throughout the layer, and the reaction product of a water-soluble nitrogenous base of high molecular weight and of a water-soluble salt of an organic polycarboxylic acid of high molecular weight interposed between and binding the fibrous and the plastic material to each other.
• the plastic material such as a thermoplastic synthetic material or latex is fixed to the fibers of the pulp by the addition of a high molecular weight, water-soluble nitrogenous base, and of a high molecular, water-soluble salt of an organic polycarboxylic acid.
• the fibrous material of the pulp may consist of naturat or synthetic cellulose fibers, or also of wood flour or of other vegetable fibers or mineral fibers, as well as of animal fibers, or fully synthetic fibers.
• the plastic material which is adhered to the fibers and incorporated in the sheet or the like which is produced according to the present invention may consist, for instance, of polyvinyl chloride, preferably of the so-called emulsion type and having a low K value, or of other polymerizates or mixed polymerizates on the basis of styrene,
• the water soluble high molecular nitrogenous bases which are preferably used according to the present invention include polyethylene imine, polypropylene imine, and polyvinyl amine.
• Water-soluble salts of high molecular organic polycarboxylic acids which give good results according to the present invention include the sodium, potassium and ammonium salts of acrylic acid, methacrylic acid, as well as mixed polymerizates of acrylic acid and acrylic acid amide which include a relatively high proportion of carboxyl groups.
• the finely subdivided preferably suspended or emulsified plastic material is fixed to the fibers of the pulp by the addition of a water-soluble nitrogenous base of high moleclar weight such as polyethylene imine and of a watersoluble salt of an organic polycarboxylic acid of high molecular weight such as a salt of polyacrylic acid.
• homologues of polyethylene imine or of polyvinyl amine may be used as the water-soluble nitrogenous base, and as water-soluble polycarboxylic acids homologues of polyacrylic acids or their mixed polymerizates or mixed condensates.
• the polyethylene imine or the like is added to the mixture of pulp and dispersed plastic material in the form of an aqueous solution and an intimate mixture of these ingredients is produced. Thereafter an aqueous solution of a water-soluble salt of polyacrylic acid or the like is added and, in this manner, the dispersed plastic material, preferably thermoplastic material, will be fixed to the fibers together with the reaction product formed of the polyethylene imine and the salt of the polyacrylic acid.
• thermoplastic material A very good retention of the thermoplastic material is obtained in this manner, with an even distribution of the thermoplastic material in the fibrous structure, as well as favorable conditions for dewatering of the thus treated pulp, for instance on a paper making machine.
• the sequence of the addition of the individual components may be varied. However, it is important that one of the two water-soluble reactants, i.e., either the salt of the polycarboxylic acid or the nitrogenous base is the last constituent added to the mixture, after other components already have been mixed well with each other.
• the precipitation reaction between the polycarboxylic acid salt and the nitrogenous base proceeds quickly and evenly, so that the process of the present invention is also suitable for being carried out in a continuous manner, provided that intensive mixing is arranged in the areas where the various ingredients are introduced into the pulp.
• the amount of precipitating agent i.e., the amount of water-insoluble reaction product formed by reaction of the nitrogenous base and the polycarboxylic acid
• the amount of precipitating agent generally will be so chosen as to correspond to an amount Cit of nitrogenous base, such as polyethylene imine which equals between 0.3 and 5% of the quantity of dispersed thermoplastic material which is to be incorporated in the finished product. It is possible, but rarely advisable, to increase the amount of polyethylene imine to more than about 5%, and preferably the amount of the water soluble nitrogenous base will be equal to between 0.5 and 2% of the weight of the thermoplastic material which is to be incorporated into the finished product.
• the amount of polycarboxylic acid preferably will be close to the stoichiometric equivalent required for reaction with the nitrogenous base.
• the optimum weight relationship will be about 1 part of polyethylene imine for 2.2 parts of polyacrylic acid.
• the amount of the polycarboxylic acid salt equals between about 60% and of the stoichiometric equivalent of the nitrogenous base present in the reaction mixture.
• a pH of between 6 and 9 is maintained in the pulp during the treatment thereof and the same pH range should also be maintained during the further processing of the treated pulp, for instance during dewatering.
• the pulp with the plastic, preferably thermoplastic, material adhering thereto is first subjected to mechanical dewatering, and subsequently to thermal dewatering which may be coupled with the application of pressure and with shaping of the material.
• the pulp concentration at the start of the treatment according to the present invention will be between O.l and 15% preferably between 2 and 6%. These ranges are preferably maintained irrespective of the specific type of fibrous material of the pulp. Of course, during subsequent working up of the treated pulp, for instance on a paper machine, it might become necessary to further dilute the pulp.
• Beating should be carried out to between 12 and 60, preferably between 25 and 40 SR.
• the proportion of plastic material, particularly synthetic thermoplastic material which is thus introduced into the paper or the like, i.e., into the fibrous mass, of which the sheet-like body is then to be formed, will be between and 80%, preferably between 40 and 60% of the total dry weight of the finished product.
• the amount of the added plastic material in the finished product will be between and 400% or preferably between 50 and 200% of the dry weight of the fibrous constituents of the finished material.
• the proportion of Watersoluble nitrogenous base which is to be added preferably will be equal to between 0.3 and 5%, and most preferably will be between 0.5 and 2% of the weight of the dispersed plastic material and, preferably, the nitrogenous base is introduced in the form of 1-5% solution thereof.
• the polycarboxylic acid salt is introduced in an amount which should be close to the stoichiometric equivalent of the nitrogenous base or within the range of between 60 and 140% of the stoichiometric equivalent.
• the manner in which the mixture which has been formed in the tank or in the hollander is worked up, particularly on a paper machine, will depend on the desired qualities of the final product. For instance, when very thin papers are to be produced, thencorresponding to the operating speed of the paper machine, and also corresponding to the desired weight per m? of the finished product, the pulp and plastic suspension will have to be more strongly diluted than would be required for producing papers of normal, i.e., somewhat higher Weight per m.'-.
• Example I A bleached mechanical pulp having a fiber density or consistency of about 5% was ground in continuous refiners or similar devices to about 25 SR. An intimate mixture was then formed in a continuous manner of the thus-treated pulp at a rate of about 4- cubic meters per hour, equal to 200 kg. of fibers per hour, and of one cubic meter per hour of a 20% dispersion of a mixed polymerizate on polyvinyl acetate basis which thus contained about 200 kg. of synthetic material per hour. Subsequently about 1.5 kg./hour of polyethylene imine dissolved in 200 liters of water were added and the thus formed mixture was passed through a pulp pump in order to obtain an even distribution of the various components of the mixture.
• the pulp mixture was diluted with water to a pulp consistency of about 2% and then, by means of an injector, about 1 mfi/hour of a 0.2% aqueous solution of the sodium salt of polyacrylic acid, equal to about 2 kg. of sodium polyacrylate per hour, were introduced.
• the aqueous solution of polyacrylic acid was adjusted to a pH of between 8 and 9.
• the thus formed mixture was then diluted to a pulp consistency of about 0.5% and subsequently worked up on a paper machine to a paper having a weight of 350 gr./m.
• the thus formed paper sheet contained about 45% per weight of the synthetic plastic material.
• Example H A mixture of pulp, of a dispersed, softened mixed polymerizate on the basis of polyvinylacetate, of polyethylene imine and of sodium polyacrylate was formed as described in Example I. The thus formed mixture was then diluted with water to a pulp consistency of 0.6%. The thus diluted and treated pulp was passed continuously to the dewatering screen of a cardboard machine. In conventional manner about 20 layers of the thus formed sheet weighing about 75 gr./m. were united on a couch cylinder. After withdrawal from the couch roller, moist plates were obtained which were then dried in a hot air tunnel. In this manner, cardboard plates were obtained having a weight of about 1500 gr./m. and containing between 40 and 42% or" the synthetic material.
• Example 111 100 kg. of unbleached mechanical pulp were sus pended in water in a concentration of 6% and beaten in a hollander to about 30 SR. Thereafter 150 kg. of emulsion type polyvinylchloride having a K value of about 60 were introduced into the hollander in the form of a fine powder and well mixed into the pulp. As further additions, 3 kg. of polyethylene imine were introduced in the form of a 1% aqueous solution, and after thorough mixing, a 0.5% aqueous solution of 6 kg. of the ammonium salt of polyacrylic acid was added.
• the thus formed mixture was then immediately worked up on a paper machine to a paper Web having a weight of 150 -gr./m.
• a size press arranged within the paper machine was used to apply an amount of dibutyl phthalate which equals 20% of the quantity of synthetic thermoplastic material which has been incorporated in the paper.
• the dibutyl phthalate was introduced at both faces of the paper web in the form of a 15% aqueous emulsion.
• the finished paper contained 55% thermoplastic material.
• 10 sheets of the thus formed paper were superposed and compressed at a pressure of kgjcm. and at a temperature of 170 C. so as to obtain a laminated structure having a density of 1.4. Due to the relatively high temperature of 170 C., gelatinization of the synthetic materials in the paper will occur and thus a substantially pore-free laminated body will be produced.
• Example IV A pulp having a consistency of 2% was formed of 30 parts per weight of asbestos fibers, 40 parts per weight of unbleached chemical wood pulp (40 SR) and 30 parts per weight of mechanical pulp.
• 150 parts (tdry substance) of a styreneacrylic acid nitrile mixed polym-erizate (:10) were added in the form of a 30% aqueous dispersion.
• a 5% aqueous solution, containing 1.5 parts per weight of polyethylene imine was added to, and thoroughly mixed with, the pulp.
• a 0.1% aqueous solution of an acrylic acid-acrylic acid amide mixed polymerizate (4: 1) including 2 parts per weight of the mixed polymerizate in the form of its sodium salt was added.
• the thus treated pulp was dewatered on a screen so as to form thereof plates having a dry weight of between 2.5 and 3 kg./m.
• the plates which were still moist were then dried and compressed in a m ulti-layer hydraulic press at a pressure of 20 kg./cm. and at a temperature of 80 C. until the plates were substantially completely dry. Thereafter, the plates were further compressed at a pressure of 50 kg./cm. and at a temperature of C. until the specific gravity of the plates had risen to 1.25.
• the thus formed plates contained.55% of the thermoplastic material and were used as lining or covering for walls, furniture or the like.
• a fibrous sheet comprising in combination, a layer of haphazardly arranged fibrous material; at least one plastic material selected from the group consisting of polyethylene, polypropylene, polyamides, polyesters, and polymerizates and mixed polymerizates of vinylchloride, vinylidenechloride, vinylacetate, vinylacetal, chloroprene, latex, styrene, butadiene, acrylic acid ester and acrlyonitrile substantially evenly distributed throughout said layer; and the reaction product of a water-soluble nitrogenous base of high molecular weight selected from the group consisting of polyethylene irnine, polypropylene imine and polyvinyl amine, and of a water-soluble salt of an organic polycarboxylic acid of high molecular weight selected from the group consisting of sodium, potassium and ammonium salts of acrylic acid and methacrylic acid, and mixed polymerizates of acrylic acid and acrylic acid amide containing a relatively large proportion of carboxyl groups interposed between and binding said
• a fibrous sheet comprising in combination, a layer of haphazardly arranged fibrous material; at least one plastic material in an at .ount equal to between about 25% and 400% of the dry weight of said fibrous material, said plastic material being selected from the group consisting of polyethylene, polypropylene, polyamides, polyesters, and polymerizates and mixed polymerizates of vinylchloride, vinylidenechloride, vinylacetate, vinylacetal, chloroprene, latex, styrene, butadiene, acrylic acid ester, and acrylonitrile substantially evenly distributed throughout said layer; and the reaction product of an amount of a water-soluble nitrogenous base of high molecular weight equal to between about 0.3 and of the Weight of said plastic material, said nitrogenous base being selected from the group consisting of polyethylene irnine, polypropylene imine and polyvinyl amine, and of an amount of a water-soluble salt of an organic polycarboxylic acid of high molecular weight equal to between about
• a fibrous sheet comprising in combination, a layer of haphazardly arranged fibrous material selected from the group consisting of animal, vegetable, mineral and synthetic organic fibers; at least one thermoplastic material in an amount equal to between about and 400% of the dry weight of said fibrous material, said plastic material being selected from the group consisting of polyethylene, polypropylene, polyamides, polyesters and polymerizates and mixed polymerizates of vinylchloride, vinylidenechloride, vinylacetate, vinylacetal, chloroprene, latex, styrene, butadiene, acrylic acid ester and acrylonitrile substantially evenly distributed throughout said layer; and the reaction product of an amount of a water-soluble nitrogenous base of high molecular weight equal to between about 0.3 and 5% of the weight of said plastic material, said nitrogenous base being selected from the group consisting of polyethylene irnine, polypropylene irnine and polyvinyl amine, and of an amount of a watersoluble salt of an organic polycar
• thermoplastic material interposed between and .adhering to the fibers of said fibrous material, the steps weight selected from the group consisting of polyethyleneimine, polypropylene imine and polyvinyl amine, and a i water-soluble salt of a polycarboxylic acid of high moleclLllBI weight selected from the group consisting of sodium, potassium and ammonium salts of acrylic acid and methacrylic acid, and mixed polymerizates of acrylic acid and acrylic acid amide containing a relatively large proportion of carboxyl groups, so as to form on said fibers a water insoluble reaction product of said nitrogenous base and said salt of a carboxylic acid, the thus formed reaction product facilitating adherence of said finely subdivided thermoplastic material to said fibers; and removing at least a portion of the water of the thus treated pulp so as to obtain a fibrous mass consisting essentially of said fibers having said thermoplastic
• a method of producing a sheet-like body consisting essentially of an intimate mixture of a fibrous material and a thermoplastic material interposed between and adhering to the fibers of said fibrous material the steps of introducing into a fibrous pulp consisting essentially of a suspension of fibers in water a finely subdivided thermoplastic material selected from the group consisting of polyethylene, polypropylene, polyamides, polyesters, and polymerizates and "mixed polymerizates of vinylchloride, vinylidenechloride, vinylacetate, vinylacetal, chloroprene, latex, styrene, butadiene, acrylic acid ester, and acrylonitrile, a water-soluble nitrogenous base of high molecular weight selected from the group consisting of polyethylene irnine, polypropylene imine and polyvinyl amine and a water-soluble salt of a polycarboxylic acid of high molecular weight selected from the group consisting of the sodium, potassium and ammonium salt
• thermoplastic material selected from the group consisting of polyethylene, polypropylene, polyamides, polyesters, and polymerizates and mixed polymerizates of vinylchloride, vinyliidenechloride, vinylacetate, vinylacetal, chloroprene, latex, styrene, butadiene, acrylic acid ester and acrylonitrile in an amount equal to between 25 and 400% of the dry weight of said fibers; a water-soluble nitrogenous base of high molecular weight selected from the group consisting of polyethylene irnine, polypropylene imine and polyvinyl amine, in an amount equal to between 0.3 and 5%
• a method of producing a sheet-lilce body consisting essentially of an intimate mixture of a fibrous material and a thermoplastic material interposed between and adhering to the fibers of said fibrous material, the steps of introducing into a fibrous pulp consisting essentially of a suspension of fibers in water having a fiber concentration of between 2-6% a finely subdivided thermoplastic material selected from the group consisting of polyethylene, polypropylene, polyamides, polyesters and polymerizates and mixed polymerizates of vinylchloride, vinylidenechloride, vinylacetate, vinylacetal, chloroprene, latex, styrene, butadiene, acrylic acid ester and acrylonitrile in an amount equal to between 50200% of the dry weight of said fibers, a Water-soluble nitrogenous base of high molecular weight selected from the group consisting of polyethylene imine, polypropylene imine and polyvinyl amine, in an amount equal to between 0.52% of the Weight of said finely sub
• thermoplastic material interposed between and adhering to the fibers of said fibrous material, the steps of introducing into a fibrous pulp consisting essentially of a suspension of fibers in water having a fiber concentration of between 0.1 and 15% a finely subdivided thermoplastic material selected from the group consisting of polyethylene, polypropylene, polyamides, polyesters and polymerizates and mixed polymerizaws of vinylchloride, vinylidenechloride, vinylacetate, vinylacetal, chloroprene, latex, styrene, butadiene, acrylic acid ester and acrylonitrile in an amount equal to between 25 and 400% of the dry Weight of said fibers, tan aqeuous solution containing between 1 and 5% of a Water-soluble nitrogenous base of high molecular Weight selected from the group consisting of polyethylene imine, polypropylene imine and polyvinyl

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Citations (4)

• 0
  • BE BE608996D patent/BE608996A/xx unknown
  • NL NL269170D patent/NL269170A/xx unknown
• 1960
  • 1960-11-04 DE DEZ8332A patent/DE1136199B/de active Pending
• 1961
  • 1961-09-07 LU LU40578D patent/LU40578A1/xx unknown
  • 1961-09-26 FI FI1683/61A patent/FI42041B/fi active
  • 1961-10-03 AT AT742161A patent/AT241262B/de active
  • 1961-10-17 FR FR876178A patent/FR1303882A/fr not_active Expired
  • 1961-10-17 GB GB37096/61A patent/GB964278A/en not_active Expired
  • 1961-10-30 CH CH1250761A patent/CH399160A/de unknown
  • 1961-11-06 US US150149A patent/US3119731A/en not_active Expired - Lifetime

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